KR100814980B1 - Vapor deposition of oxides, silicates, and phosphates - Google Patents
Vapor deposition of oxides, silicates, and phosphates Download PDFInfo
- Publication number
- KR100814980B1 KR100814980B1 KR1020077024096A KR20077024096A KR100814980B1 KR 100814980 B1 KR100814980 B1 KR 100814980B1 KR 1020077024096 A KR1020077024096 A KR 1020077024096A KR 20077024096 A KR20077024096 A KR 20077024096A KR 100814980 B1 KR100814980 B1 KR 100814980B1
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- KR
- South Korea
- Prior art keywords
- metal
- vapor
- ald
- precursor
- silicon
- Prior art date
Links
- 235000021317 phosphate Nutrition 0.000 title abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 title abstract description 17
- 150000003013 phosphoric acid derivatives Chemical class 0.000 title abstract description 10
- 238000007740 vapor deposition Methods 0.000 title abstract 2
- 150000004760 silicates Chemical class 0.000 title description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 150000001408 amides Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 125000003368 amide group Chemical group 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 37
- 229910052914 metal silicate Inorganic materials 0.000 abstract description 21
- 229910052735 hafnium Inorganic materials 0.000 abstract description 19
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 abstract description 19
- 239000012528 membrane Substances 0.000 abstract description 19
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 15
- -1 alkoxy silanol Chemical compound 0.000 abstract description 14
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001463 metal phosphate Inorganic materials 0.000 abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 10
- HLDBBQREZCVBMA-UHFFFAOYSA-N hydroxy-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](O)(OC(C)(C)C)OC(C)(C)C HLDBBQREZCVBMA-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 abstract description 10
- WZPMZMCZAGFKOC-UHFFFAOYSA-N diisopropyl hydrogen phosphate Chemical compound CC(C)OP(O)(=O)OC(C)C WZPMZMCZAGFKOC-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 abstract description 9
- 229910001386 lithium phosphate Inorganic materials 0.000 abstract description 8
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 abstract description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 8
- 150000004703 alkoxides Chemical class 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052744 lithium Inorganic materials 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000012707 chemical precursor Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 65
- 238000000231 atomic layer deposition Methods 0.000 description 58
- 239000010408 film Substances 0.000 description 46
- 238000001556 precipitation Methods 0.000 description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 34
- 239000000376 reactant Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 238000005229 chemical vapour deposition Methods 0.000 description 32
- 229910052710 silicon Inorganic materials 0.000 description 31
- 239000010703 silicon Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 20
- 239000012159 carrier gas Substances 0.000 description 19
- 150000002736 metal compounds Chemical class 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- 239000007983 Tris buffer Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 229910000449 hafnium oxide Inorganic materials 0.000 description 12
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 12
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- 239000011574 phosphorus Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000012716 precipitator Substances 0.000 description 11
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 11
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 10
- 239000010452 phosphate Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052752 metalloid Inorganic materials 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 8
- 239000012686 silicon precursor Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 7
- 150000002737 metalloid compounds Chemical class 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 6
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 150000002902 organometallic compounds Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000002738 metalloids Chemical class 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 238000001028 reflection method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000006557 surface reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910020175 SiOH Inorganic materials 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 4
- 230000032258 transport Effects 0.000 description 4
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- ORJFXWYTRPGGRK-UHFFFAOYSA-N hydroxy-tris(2-methylbutan-2-yloxy)silane Chemical compound CCC(C)(C)O[Si](O)(OC(C)(C)CC)OC(C)(C)CC ORJFXWYTRPGGRK-UHFFFAOYSA-N 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KCIKCCHXZMLVDE-UHFFFAOYSA-N silanediol Chemical compound O[SiH2]O KCIKCCHXZMLVDE-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 3
- MWQKURVBJZAOSC-UHFFFAOYSA-N 1-propan-2-ylcyclopenta-1,3-diene Chemical compound CC(C)C1=CC=CC1 MWQKURVBJZAOSC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 101100007427 Manduca sexta COVA gene Proteins 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910006249 ZrSi Inorganic materials 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- JGZUJELGSMSOID-UHFFFAOYSA-N dialuminum;dimethylazanide Chemical compound CN(C)[Al](N(C)C)N(C)C.CN(C)[Al](N(C)C)N(C)C JGZUJELGSMSOID-UHFFFAOYSA-N 0.000 description 2
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000012705 liquid precursor Substances 0.000 description 2
- AXPPAKIFWZPHCR-UHFFFAOYSA-N lithium;bis[ethyl(dimethyl)silyl]azanide Chemical compound [Li+].CC[Si](C)(C)[N-][Si](C)(C)CC AXPPAKIFWZPHCR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- 239000012688 phosphorus precursor Substances 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical class ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004819 silanols Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- CHEANNSDVJOIBS-MHZLTWQESA-N (3s)-3-cyclopropyl-3-[3-[[3-(5,5-dimethylcyclopenten-1-yl)-4-(2-fluoro-5-methoxyphenyl)phenyl]methoxy]phenyl]propanoic acid Chemical compound COC1=CC=C(F)C(C=2C(=CC(COC=3C=C(C=CC=3)[C@@H](CC(O)=O)C3CC3)=CC=2)C=2C(CCC=2)(C)C)=C1 CHEANNSDVJOIBS-MHZLTWQESA-N 0.000 description 1
- VDIFBZPOGJKQQR-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-propan-2-ylcyclopenta-1,3-diene Chemical compound CC(C)C1C(C)=C(C)C(C)=C1C VDIFBZPOGJKQQR-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- FTFYDDRPCCMKBT-UHFFFAOYSA-N 1-butylcyclopenta-1,3-diene Chemical compound CCCCC1=CC=CC1 FTFYDDRPCCMKBT-UHFFFAOYSA-N 0.000 description 1
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- NEVPZIBSIIDIRE-UHFFFAOYSA-N 1-methylnaphthalene;hydrate Chemical class O.C1=CC=C2C(C)=CC=CC2=C1 NEVPZIBSIIDIRE-UHFFFAOYSA-N 0.000 description 1
- RZPAXISDLOEXPI-UHFFFAOYSA-N 1-propylcyclopenta-1,3-diene Chemical compound CCCC1=CC=CC1 RZPAXISDLOEXPI-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WQJRXDQQOXLGGE-UHFFFAOYSA-N C(C)[SiH](C)[N-][SiH](CC)C.[Li+] Chemical compound C(C)[SiH](C)[N-][SiH](CC)C.[Li+] WQJRXDQQOXLGGE-UHFFFAOYSA-N 0.000 description 1
- XWVMGDDMXTWPGA-UHFFFAOYSA-N CCC1=CC=CC=[C-]1 Chemical class CCC1=CC=CC=[C-]1 XWVMGDDMXTWPGA-UHFFFAOYSA-N 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
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Images
Classifications
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- H01L21/02159—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing zirconium, e.g. ZrSiOx
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Abstract
금속 규산염 또는 인산염들은, 알콕시 실라놀 또는 알킬 포스페이트의 증기와 반응성 있는 금속 아마이드,알킬 또는 알콕사이드와의 반응에 의해 가열된 기질상에 석출되어 진다. 예를 들면, 트리스(tert-부톡시)실라놀의 증기와 테트라키스 (에틸메틸아미도)하프늄의 증기가 반응하여 300℃로 가열된 표면위에서 하프늄규산염을 석출시킨다. 생성된 막은 반응기 전체를 통해 매우 균일한 화학양론을 갖는다. 이와 유사하게, 디이소프로필 포스페이트의 증기는 리튬비스(에틸메틸아미도)아마이드의 증기와 반응하여 250℃로 가열된 표면위에서 리튬인산염을 석출시킨다.
증기 펄스들을 교대로 공급함으로써, 매우 균일한 두께 분포와 탁월한 단계적 피막을 갖는 상기와 합성물이 생산된다.
증기 석출, CVD, ALD, 휘발성 화학 전구체, 금속 규산염, 금속 인산염, 하프늄,이트륨, 지르코늄, 란탄
Metal silicates or phosphates are precipitated on a heated substrate by reaction with metal amides, alkyls or alkoxides reactive with vapors of alkoxy silanol or alkyl phosphates. For example, a vapor of tris (tert-butoxy) silanol and a vapor of tetrakis (ethylmethylamido) hafnium react to precipitate hafnium silicate on a surface heated to 300 ° C. The resulting membrane has a very uniform stoichiometry throughout the reactor. Similarly, the vapor of diisopropyl phosphate reacts with the vapor of lithium bis (ethylmethylamido) amide to precipitate lithium phosphate on a surface heated to 250 ° C.
By alternately supplying steam pulses, the above and the composites are produced with a very uniform thickness distribution and an excellent stepwise coating.
Vapor deposition, CVD, ALD, volatile chemical precursors, metal silicates, metal phosphates, hafnium, yttrium, zirconium, lanthanum
Description
본 발명은 화학 증기 석출(CVD), 원자층 석출(ALD)과 같은 박막 석출 과정에서 사용되는 신규한 시약에 관한 것이다. 이 시약들은 금속 산화물, 규산염, 금속 인산화물, 이산화 규소라고 흔히 부르는 금속 및/또는 산소와 함께, 규소 및/또는 인산을 포함하는 물질의 석출에 사용되어 질 수 있다.The present invention relates to novel reagents used in thin film deposition processes such as chemical vapor deposition (CVD) and atomic layer deposition (ALD). These reagents may be used for the precipitation of materials containing silicon and / or phosphoric acid, together with metals and / or oxygen commonly referred to as metal oxides, silicates, metal phosphates, silicon dioxides.
화학 증기 석출(CVD)은 증기 상태의 반응물로부터 도료나 분말과 같은 고체 물질을 형성하는 널리 사용되는 과정이다. CVD과정의 종합적인 개관은 최근에 CVD of Nonmetals,W.S.Rees,Jr.,Editor,VCH Publisher,Weinheim,Germany,1996년; CVD of Compound of semiconductors,A.C.Jones and P.O'Brien,VHC,1996년; 및 The Chemistry of Metal CVD, T.Kodas and M.hampden-Smith,Editors,VCH,1994년에 주어져 있다.Chemical vapor deposition (CVD) is a widely used process for forming solid materials such as paints and powders from vapor reactants. A comprehensive overview of the CVD process has been recently published in the CVD of Nonmetals , WS Rees, Jr., Editor, VCH Publisher, Weinheim, Germany, 1996; CVD of Compound of semiconductors , AC Jones and P. O'Brien, VHC, 1996; And The Chemistry of Metal CVD , T. Kodas and M. hampden-Smith, Editors, VCH, 1994.
CVD과정에서 반응물 증기 또는 증기 혼합물은 박막이 석출될 기질의 가열된 표면과 접촉하게 된다. CVD의 형태와 관련하여, 두 반응물 증기들이 교대로 가열된 표면에 노출된다. 이러한 형태의 CVD는 종종 원자층 석출(ALD)이라고 불린다. 적당한 반응물로서, ALD는 혼합 증기를 이용한 CVD에 비하여 향상된 단계적 피복률과 두께의 균일성을 제공한다, ALD의 개관에 관하여는, Miko Ritala의 Applied Surface Science , 112권, 223-230페이지(1997년)에 나타난다.During CVD the reactant vapor or vapor mixture comes into contact with the heated surface of the substrate on which the thin film will be deposited. With regard to the form of CVD, two reactant vapors are exposed to alternatingly heated surfaces. This type of CVD is often referred to as atomic layer precipitation (ALD). As a suitable reactant, ALD provides improved step coverage and thickness compared to CVD with mixed vapors. Provides uniformity, as for the overview of the ALD, by Miko Ritala Applied Surface Science , Vol . 112, pp. 223-230 (1997).
금속 규산염의 피막들은 많은 응용예와 잠재적 응용예을 갖는다. 예를 들면, 지르코늄, 하프늄, 이트륨, 란탄의 규산염들은 실리콘 반도체 기술에서 게이트 절연체로서의 이산화규소의 대체물로서의 가능성이 고려되고 있다. A.Kingon 등의 Nature,(406권,1032-1038페이지,(2000년))에서 그 예를 볼 수 있다: Science(288권,319-321페이지(2000년))에서, Ritala 등은 지르코늄 규산염을 포함한 금속 규산염을 생산하기 위한 금속 염화물과 규소 알콕사이드의 연쇄적인 ALD반응의 이용에 관한 보고를 하였다. 그러나 이러한 방법은 막에 염소 잔여물을 남기고 이것은 막의 질(property)을 떨어뜨릴 뿐 아니라 기질이나 이후의 피막의 점착성에도 좋지 않다. 전구체에서 염소는 금속 기질 또는 석출에 이용되는 기구들을 부식시킬 수 있다. 따라서 금속 규산물이나 금속 산화물의 CVD 또는 ALD를 위한 무염소 전구체(chlorine-free precusor)를 가지는 것은 유용하다.Coatings of metal silicates have many and potential applications. For example, the silicates of zirconium, hafnium, yttrium and lanthanum are being considered as a substitute for silicon dioxide as a gate insulator in silicon semiconductor technology. For example, A. Kingon et al. , Nature , (406, 1032-1038, (2000)): Science (Vol. 288, pp. 319-321 (2000)), Ritala et al. A report has been made on the use of the chain ALD reaction of metal chlorides and silicon alkoxides to produce metal silicates. However, this method leaves chlorine residues on the membrane, which not only degrades the membrane property, but also is not good for the adhesion of the substrate or subsequent coatings. Chlorine in the precursor can corrode metal substrates or instruments used for precipitation. Therefore, it is useful to have a chlorine-free precusor for CVD or ALD of metal silicates or metal oxides.
이산화 규소의 ALD는 Klaus 등의 미국 특허 6,090,442(2000년)에 의해 이루어져 왔으나 그 석출 속도는 매우 느리고, 기질 온도가 상온에 가까운 값으로 제한 되었다.ALD of silicon dioxide has been made by US Pat. No. 6,090,442 (2000) to Klaus et al., But the deposition rate is very slow and the substrate temperature is limited to near room temperature.
리튬 인산염은 최근 리튬 이온 반도체나 리튬 배터리로 관심의 대상이 되고 있는 재료이다. 현재 리튬 인산염의 CVD나 ALD의 과정에 대하여는 알려진 바가 없다.Lithium phosphate is a material of interest recently as a lithium ion semiconductor or a lithium battery. At present, there is no known process of CVD or ALD of lithium phosphate.
본 발명의 중요한 특징은 금속 규산염, 인산염 또는 산화물의 CVD나 ALD에 적용되는 반응성을 갖는 휘발성 화학 전구체를 포함한 것이다.An important feature of the present invention is the inclusion of volatile chemical precursors having reactivity applied to CVD or ALD of metal silicates, phosphates or oxides.
상기 화학적 전구체의 이점은 이들이 염소를 포함하지 않기 때문에, 금속 규산염, 인산염, 산화물의 CVD 또는 ALD의 과정에서 염소 잔여물을 남기지 않는다는 것이다.The advantage of these chemical precursors is that since they do not contain chlorine, they do not leave chlorine residues in the course of CVD or ALD of metal silicates, phosphates, oxides.
본 발명과 관련한 특징은 규소 기질과 석출된 금속 규산염 사이의 예리한 경계면을 형성하는 조건하에서의 금속 규산염의 석출이다.A feature associated with the present invention is the precipitation of metal silicates under conditions that form a sharp interface between the silicon substrate and the precipitated metal silicates.
상기 공정의 장점은 가열된 기질의 표면으로 운반되기 이전에 모든 반응물이 균질하게 혼합될 수 있는 CVD공정에 의한 금속 규산염이나 인산염의 석출을 가능하게 한다는 점이다.The advantage of this process is that it allows the precipitation of metal silicates or phosphates by a CVD process where all reactants can be homogeneously mixed before being transported to the surface of the heated substrate.
상기 방법의 추가적 장점은 반응물의 농도 또는 반응기내에서의 기질 위치와 같은 조건의 임의의 범위에 걸쳐, 규소에 대한 상대적으로 고정된 금속의 비율로 금속 규산염이나 인산염을 증착하는 것이다.A further advantage of the method is the deposition of metal silicates or phosphates in a proportion of relatively fixed metal to silicon over any range of conditions, such as the concentration of the reactants or the position of the substrate in the reactor.
본 발명의 다른 이점은 좁은 구멍, 트렌치(trench), 또는 다른 구조물을 가진 등각의 코팅을 할 수 있다는 것이다. 이 능력은 통상 우수한 단계적 피복(step coverage)으로 알려져 있다.Another advantage of the present invention is the ability to conformal coating with narrow holes, trenches, or other structures. This capability is commonly known as good step coverage.
본 발명의 또다른 특징은 리튬 인산염을 포함하는 물질의 제조를 할 수 있다는 것이다.Another feature of the present invention is that it is possible to prepare materials comprising lithium phosphate.
본 발명의 장점은 반응물이 안정하고 비교적 덜 위험하다는 것이다.An advantage of the present invention is that the reactants are stable and relatively less dangerous.
본 발명의 또다른 특징은 금속 산화물 또는 금속 산화물의 혼합물을 위한 화학 증기석출 또는 원자층 석출 과정을 포함한다.Another feature of the present invention includes a chemical vapor deposition or atomic layer deposition process for metal oxides or mixtures of metal oxides.
본 발명의 그밖의 특징은 이산화 규소의 화학 증기 석출 또는 원자층 석출과정을 포함한다.Other features of the present invention include chemical vapor deposition or atomic layer precipitation of silicon dioxide.
본 발명의 특이한 점의 하나는 마이크로 전자 장치에서의 게이트 절연체나 트렌치 축전기로서 유용한 높은 유전 상수를 갖는 지르코늄, 하프늄, 이트륨 및/또는 란탄의 산화물 또는 규산염의 석출 과정을 포함한다는 것이다. One particular aspect of the present invention involves the precipitation of oxides or silicates of zirconium, hafnium, yttrium and / or lanthanum with high dielectric constants useful as gate insulators or trench capacitors in microelectronic devices.
본 발명의 다른 특징은 평면 도파관(waveguide), 멀티플렉서(multiplexer)/디멀티플렉서(dimultiplexer), 광학 간섭 여광기에서처럼 유용한 광학 활성을 갖는 이산화 규소나 금속 규산염을 석출하는 과정을 포함하는 것이다.Another feature of the present invention includes the precipitation of silicon dioxide or metal silicates with useful optical activity, such as in planar waveguides, multiplexers / dimultiplexers, optical interference filters.
본 발명의 그 밖의 특징은 전지 또는 전자 장치(electronic device)의 격리자(seperator)로 사용되는 리튬의 빠른 확산을 가능하게 하는 리튬 인산염의 석출방법을 포함한다는 것이다. Another feature of the present invention is that it includes a method of depositing lithium phosphate that allows for the rapid diffusion of lithium used as a separator in a battery or an electronic device.
본 발명의 다른 특징이자 장점은 본 발명을 읽는 이 분야의 당업자에게 명백하다는 점이다.Other features and advantages of the present invention are apparent to those skilled in the art upon reading the present invention.
본 발명의 한 측면에서 알콕시실라놀(alkoxysilanol)의 증기는 금속 또는 메탈로이드의 알킬아마이드 또는 알킬 또는 사이클로 펜타디에닐과 같은 적당히 반응성 있는 금속 또는 메탈로이드 화합물의 증기와 반응한다. 이 반응은 막을 형성하는 방식으로 진행될 수 있다.In one aspect of the invention the vapor of alkoxysilanol is reacted with the vapor of a suitably reactive metal or metalloid compound, such as alkylamides of metals or metalloids or alkyl or cyclopentadienyl. This reaction can proceed in a manner that forms a film.
적어도 몇몇의 구현예에서, 트리스(알콕시)실라놀 화합물은 하기 식을 갖는데, 이 때 Rn은 수소, 알킬기, 플루오르 알킬기 또는 바람직하게는 화합물의 휘발성을 높이기 위해 선택된 다른 원자 또는 기들로 치환된 알킬기이며, Rn은 R1 내지 R9중의 어느 하나이다. 각각의 Rn은 서로 동일하거나 상이할 수 있다.In at least some embodiments, the tris (alkoxy) silanol compound has the formula wherein R n is hydrogen, an alkyl group, a fluoroalkyl group or an alkyl group substituted with other atoms or groups preferably selected to increase the volatility of the compound R n is R 1 To R 9 . Each R n may be the same or different from each other.
적어도 몇몇의 구현예에서 메틸기는 위에서 주어진 화학식1의 Rn 각각으로부터 선택될 경우, 보다 바람직한 화합물인 트리스(tert-부톡시)실라놀(화학식2)을 얻을 수 있으며, 보다 간단하게 (tBuO)3SiOH로 쓰여질 수 있다.In at least some embodiments the methyl group is R n of Formula 1 given above When selected from each, a more preferred compound tris ( tert -butoxy) silanol (Formula 2) can be obtained and more simply written as ( t BuO) 3 SiOH.
본 발명의 다른 화합물은 트리스(tert -아밀옥시)실라놀(화학식3)이라고도 알려진, 트리스(tert-펜틸옥시)실라놀인데 보다 간단히 (tAmO)3SiOH로 쓸 수 있다.Another compound of the present invention is tris ( tert - pentyloxy) silanol, also known as tris ( tert -amyloxy) silanol (Formula 3), which can be written simply ( t AmO) 3 SiOH.
어떤 구현예에서 트리스(알콕시)실라놀 화합물보다 덜 안정함에도 불구하고, 적어도 본 발명의 몇몇의 구현예에서는 (tBuO)2Si(OH)2와 같은 디(알콕시)실란디올 이 사용될 수 있다. 일반적으로 화학식4를 갖는 디(알콕시)실란디올은 본 발명에서 사용될 것인데, Rn은 수소, 알킬기, 플루오르 알킬기 또는 바람직하게는 화합물 의 휘발성과 안정성을 높이기 위해 선택된 다른 원자들 또는 기로 치환된 알킬기이며, Rn은 R1 내지 R6중의 어느 하나이다. Rn은 서로 동일하거나 상이할 수 있다.Although in some embodiments less stable than tris (alkoxy) silanol compounds, in at least some embodiments of the invention, di (alkoxy) silanediol such as ( t BuO) 2 Si (OH) 2 may be used. In general, di (alkoxy) silanediol having the formula (4) will be used in the present invention, R n is hydrogen, an alkyl group, a fluoroalkyl group or an alkyl group substituted with other atoms or groups preferably selected to increase the volatility and stability of the compound , R n is any one of R 1 to R 6 . R n may be the same or different from each other.
적어도 몇몇의 구현예에서 화학식1의 R1 또는 화학식4의 R1-R6 은 수소, 메틸, 에칠, n-프로필, 이소프로필로 구성된 그룹에서 선택된 것일 것이다.In at least some embodiments R 1 of Formula 1 or R 1 -R 6 of Formula 4 will be selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl.
앞서 말한 화합물에서, 일반적 구조의 R1 내지 R9의 알킬기 또는 화학식4의 R1 내지 R6은 아릴, 알케닐, 알키닐기와 같은 어느 정도의 불포화도를 갖는 탄화수소로 이해될 수 있다.In the aforementioned compounds, R 1 of the general structure Or an alkyl group of R 9 or R 1 to R 6 of formula 4 may be understood as a hydrocarbon having some degree of unsaturation such as aryl, alkenyl, alkynyl group.
어떤 구현예에서 금속 화합물은 실라놀의 약산성의 프로톤(slightly acidic proton)과 쉽게 반응하는 것들을 포함한다. 이들 산성 프로톤은 실라놀의 산소에 직접 결합된 것이다. 이러한 산성 프로톤과 일반적으로 결합하는 금속 화합물은 대부분의 금속 알킬과 다른 유기금속 화합물, 금속 알킬아마이드, 임의의 금속 알콕사이드류를 포함한다. 어떤 특정 화합물의 반응성은 그것을 알콕시실라놀과 섞고, 그 혼합물을 핵자기 공명 진단 장치(NMR)로 분석함으로써 쉽게 확인할 수 있 다. 본 발명의 발명자들은 물과 반응하는 것으로 알려진 화합물이 일반적으로 알콕시실라놀과도 반응하는 것을 발견하였다.In certain embodiments, metal compounds include those that readily react with the lightly acidic protons of silanol. These acidic protons are bound directly to the oxygen of silanol. Metal compounds generally associated with these acidic protons include most metal alkyls and other organometallic compounds, metal alkylamides, and any metal alkoxides. The reactivity of a particular compound can be easily identified by mixing it with alkoxysilanol and analyzing the mixture with a nuclear magnetic resonance diagnostic device (NMR). The inventors of the present invention have found that compounds known to react with water generally also react with alkoxysilanol.
또한 본 발명자들은 석출된 금속 규산염의 화학양론을 조절할 수 있음을 알아냈다. 규소/금속 비율은 실라놀의 일부 또는 모두를 물이나 알코올로 대체함으로써 감소될 수 있다. 역으로, 규소/금속 비율은 금속 공급원의 전부 또는 일부를 실리콘 아마이드나 실릴렌과 같은 적절한 활성이 있는 화합물로 대체함으로써 증가시킬 수 있다. 이러한 방법들을 통해 석출된 물질의 구조를 순수한 금속에서부터 순수한 이산화 규소까지 원하는 어떠한 규소/산소 비율로 선택할 수 있다. 화학양론은 석출 과정에 따라 변할 수 있다. 예를 들면,규소 반도체 장치를 위한 게이트 절연체의 석출에서는, 계면의 전기적 특성을 향상시키기 위해 규소가 풍부한 층을 규소 표면에 근접시켜 석출하고, 이어서 높은 유전 상수를 갖는 금속이 풍부한 층을 석출한다.The inventors also found that the stoichiometry of the precipitated metal silicates can be controlled. The silicon / metal ratio can be reduced by replacing some or all of the silanol with water or alcohol. Conversely, the silicon / metal ratio can be increased by replacing all or part of the metal source with a suitable active compound, such as silicon amide or silylene. These methods allow the structure of the precipitated material to be selected at any desired silicon / oxygen ratio, from pure metals to pure silicon dioxide. The stoichiometry can change depending on the precipitation process. For example, in the deposition of a gate insulator for a silicon semiconductor device, in order to improve the electrical properties of the interface, a silicon-rich layer is deposited close to the silicon surface, and then a metal-rich layer having a high dielectric constant is deposited.
발명의 다른 측면에서는 비스(알킬)포스페이트의 증기가 금속 알킬 아마이드, 금속 알킬, 금속 사이클로 펜타디에나이드 또는 금속 알콕사이드와 같은 반응성 있는 금속 화합물의 증기와 반응하여, 금속 인산염을 형성한다. 이 반응은 막을 형성하는 방식으로 진행될 수 있다.In another aspect of the invention, a vapor of bis (alkyl) phosphate is reacted with a vapor of a reactive metal compound such as metal alkyl amide, metal alkyl, metal cyclo pentadiene or metal alkoxide to form metal phosphate. This reaction can proceed in a manner that forms a film.
본 발명의 최소한 몇몇의 구현예에서, 인을 포함한 전구체들은 비스(알킬)포스페이트를 포함하며, 여기서 Rn은 수소, 알킬기, 플루오르 알킬기 또는 다른 원자들 또는 기로 치환된 알킬기이며, Rn은 R1 내지 R6중의 어느 하나이다. 각각의 Rn 은 서로 동일하거나 상이할 수 있다.In at least some embodiments of the invention, the precursors comprising phosphorus comprise bis (alkyl) phosphates, wherein R n is hydrogen, an alkyl group, a fluoroalkyl group or an alkyl group substituted with other atoms or groups, and R n is R 1 To R 6 . Each R n may be the same or different from each other.
하나 이상의 구현예에서, 인 전구체는 화학식6으로 나타내어 지는 디이소프로필 포스페이트이다.In one or more embodiments, the phosphorus precursor is diisopropyl phosphate represented by formula (6).
금속 인산염의 화학량론을 조절하는 것 또한 가능하다. 인/금속 비율은 비스(알킬)포스페이트의 일부 또는 전부를 물 또는 알코올로 치환함으로써 감소시킬 수 있다. 역으로, 인/금속 비율은 적절한 인의 공급원으로 금속의 공급원의 일부 또는 전부를 치환함으로써 증가시킬 수 있다. 이러한 방법을 통해, 석출된 물질의 조성은 순수한 금속 산화물에서 인 산화물 또는 임의의 원하는 인/금속 비율을 갖 는 것으로 다양하게 만들어 낼 수 있다.It is also possible to adjust the stoichiometry of the metal phosphate. The phosphorus / metal ratio can be reduced by substituting some or all of the bis (alkyl) phosphate with water or alcohols. Conversely, the phosphorus / metal ratio can be increased by replacing some or all of the source of metal with a suitable source of phosphorus. In this way, the composition of the precipitated material can vary from pure metal oxide to phosphorus oxide or to any desired phosphorus / metal ratio.
어떤 구현예에서는 일반적 구조5의 R1-R6 기는 수소, 메틸, 에틸, n-프로필 또는 이소프로필기로 구성된 그룹에서 선택될 수 있다. 전술한 화합물에 있어 화학식1의 알킬기 R1-R9 또는 화학식4의 R1-R6는, 예를 들어 아릴, 알케닐, 또는 알키닐기 정도의 불포화도를 갖는 탄화수소일 것이다.In certain embodiments, the R 1 -R 6 groups of general structure 5 can be selected from the group consisting of hydrogen, methyl, ethyl, n-propyl or isopropyl groups. Alkyl group of formula 1 R 1 -R 9 in the compound Or R 1 -R 6 of formula (4), for example, will be a hydrocarbon having an unsaturation degree of about aryl, alkenyl, or alkynyl group.
본 발명의 다른 측면에서, 규소를 포함한 재료의 제조 방법에는 기질을 알콕시실라놀, 알콕실란디올 및 실릴렌(silylene)으로 구성된 군으로부터 선택된 하나 또는 그 이상의 증기에 노출시키는 과정을 포함한다. 최소한 어떤 구현예에서, 실릴렌은 하기 구조이며, R은 알킬기 또는 tert-부틸이다.In another aspect of the invention, a method of making a material comprising silicon includes exposing the substrate to one or more vapors selected from the group consisting of alkoxysilanol, alkoxysilanediol and silylene. In at least some embodiments, the silylene is of the structure wherein R is an alkyl group or tert -butyl.
본 발명의 한 측면에서 , 인을 포함하는 재료의 제조 방법은 기질을 비스포스페이트, 인(Ⅲ)산화물 및 백인(white phosphorus)으로 구성된 군에서 선택된 하나 또는 그 이상의 증기에 노출시키는 과정을 포함한다.In one aspect of the invention, a method of making a material comprising phosphorus comprises exposing the substrate to one or more vapors selected from the group consisting of bisphosphates, phosphorus (III) oxides and white phosphorus.
본 발명의 다른 측면에서, 벤젠 수화물, 나프탈렌 수화물, 또는 치환된 벤젠 수화물, 치환된 나프탈렌 수화물과 같은 아렌 수화물로 구성된 군으로부터 선택된 1이상의 증기에 기질을 노출시키는 것을 포함하는 산소-포함 재료의 제조에 본 방법은 제공될 수 있다.In another aspect of the invention, in the manufacture of an oxygen-containing material comprising exposing a substrate to at least one vapor selected from the group consisting of benzene hydrate, naphthalene hydrate, or arene hydrate such as substituted benzene hydrate, substituted naphthalene hydrate. The method can be provided.
본 발명의 다른 측면에서 금속 산화물을 형성하는 과정은 교대로 가열된 표면을 1이상의 금속 아마이드에 노출시킨 후 물이나 알코올의 증기에 노출시키는 단계를 포함한다.In another aspect of the invention, the process of forming a metal oxide includes exposing the alternately heated surfaces to one or more metal amides followed by exposure to water or a vapor of alcohol.
최소한 어떤 구현에에서, 알코올은 아렌 수화물이고, 또는 어떤 구현예에서는 표 1로부터 금속 아마이드 또는 아마이드는 선택될 수 있다.In at least some embodiments, the alcohol is an arene hydrate, or in some embodiments a metal amide or amide may be selected from Table 1.
본 발명의 다른 측면에서 산소 및 1이상의 금속을 포함하는 재료를 형성하는 방법은 하나 또는 그 이상의 유기금속 화합물의 증기와 아렌 수화물의 증기에 교대로 표면을 노출시키는 단계를 포함한다.In another aspect of the invention, a method of forming a material comprising oxygen and at least one metal comprises alternately exposing the surface to a vapor of one or more organometallic compounds and a vapor of arene hydrate.
최소한 한 구현예에서, 유기금속 화합물은 표 2에서 선택되어 진다.In at least one embodiment, the organometallic compound is selected from Table 2.
1.금속 규산염과 이산화 규소1.Metal Silicate and Silicon Dioxide
본 발명은 금속과 규소의 함량이 변화하는 금속 규산염을 제조하는 방법을 제공한다. 상기 방법은 알콕시실라놀 또는 알콕실란디올의 증기와, 1이상의 금속 또는 메탈로이드 화합물과의 반응을 수반한다. 화합물은 기질 위에서, 분말 또는 막으로 형성될 수 있고, 임의의 구현예에서는 가열된 기질상에 형성될 수 있다. 그 화합물은 기질상에서 석출되기 이전에 알콕실라놀 또는 알콕실란디올의 증기와 금속 또는 메탈로이드 화합물을 혼합함으로써 기질위에 형성될 수 있다. 최소한 한 구현예에서는 기질은 알콕실라놀이나 알콕실란디올 증기와 하나 이상의 금속이나 메탈로이드 화합물 증기에 교대로 노출되어 진다.The present invention provides a method for producing a metal silicate in which the content of metal and silicon is varied. The process involves the reaction of a vapor of alkoxysilanol or alkoxysilanediol with at least one metal or metalloid compound. The compound may be formed on the substrate, as a powder or a film, and in some embodiments may be formed on a heated substrate. The compound may be formed on the substrate by mixing a metal or metalloid compound with a vapor of alkoxylanol or alkoxysilanediol prior to precipitation on the substrate. In at least one embodiment, the substrate is exposed to alternating alkoxylanol or alkoxysilanediol vapors and one or more metal or metalloid compound vapors.
실라놀과 실란디올 반응물은 상업적으로 사용가능한, 종래 또는 과거의 기술을 사용하여 제조될 수 있다. 규소 전구체 ,트리스(tert-부톡시)실라놀은 Aldrich Chemical Company(Milwaukee,WI)와 Gelest,Inc.(Tullytown,PA)로부터 사용가능하다. 트리스(tert-부톡시)실라놀은 이하의 두 반응 중 어느 것에 의해 만들어 질 수 있다.Silanol and silanediol reactants may be prepared using commercially available, conventional or past techniques. Silicon precursor, tris ( tert -butoxy) silanol, is available from Aldrich Chemical Company (Milwaukee, WI) and Gelest, Inc. (Tullytown, PA). Tris ( tert -butoxy) silanol can be made by either of the following two reactions.
SiCl4 + 3tBuOH → (tBuO)3SiCl + 3HCl (1)SiCl 4 + 3 t BuOH → ( t BuO) 3 SiCl + 3 HCl (1)
SiCl4 + 3NaOtBu → (tBuO)3SiCl +3 NaCl (2)SiCl 4 + 3 NaO t Bu → ( t BuO) 3 SiCl +3 NaCl (2)
트리스(tert-부톡시)클로로실란은 이어서, 다음 반응에 의해 가수분해되어진다.Tris ( tert -butoxy) chlorosilane is then hydrolyzed by the following reaction.
(tBuO)3SiCl + H2O → (tBuO)3SiOH + HCl (3)( t BuO) 3 SiCl + H 2 O → ( t BuO) 3 SiOH + HCl (3)
Backer 등의, Rec . Trav . Chim.,61권, 500페이지(1942년)에서 볼 수 있다. 이 화합물은 상온에서 고체이고 약66℃에서 녹는다. 약 10- 4토르(Torr)의 낮은 압력에서는 상온에서 승화하고, 200토르(Torr)압력에서는 약104℃에서 증류될 수 있다. 메시틸렌(mesitylene) 또는 테트라데칸(tetradecane)과 같은 유기 용매에서 매우 잘 용해되고, 그 증기는 순간적인 기화(flash vaporization)에 의해 용이하게 형성될 수 있다.Backer et al., Rec . Trav . Chim ., 61, 500 pages (1942). This compound is solid at room temperature and melts at about 66 ° C. In the low pressure of about 104 Torr (Torr), and sublimation at room temperature and 200 Torr (Torr) pressure it can be distilled at about 104 ℃. It dissolves very well in organic solvents such as mesitylene or tetratradecane, and its vapor can be easily formed by flash vaporization.
다른 트리스(tert-알콕시)실라놀은 tert -부탄올 대신, tert -펜틸 알코 올(tert-아밀 알코올로도 알려짐)과 같은 다른 3차 알코올을 사용하여, 비슷한 반응 과정에 의해 제조될 수 있을 것이다. 트리스(tert-아밀옥시)실라놀,Other tris ( tert -alkoxy) silanols may be prepared by similar reaction processes, using other tertiary alcohols such as tert - pentyl alcohol (also known as tert -amyl alcohol) instead of tert - butanol. Tris ( tert -amyloxy) silanol,
(tAmO)3SiOH은 상온에서 액체이며 그 액체의 순간적인 기화에 의해 용이하게 증기를 얻을 수 있다. 상기 증기는 96℃에서 약 2토르의 증기압을 갖는다. Aldrich( t AmO) 3 SiOH is a liquid at room temperature, and vapor can be easily obtained by instantaneous vaporization of the liquid. The vapor has a vapor pressure of about 2 Torr at 96 ° C. Aldrich
*Chemical사로부터 상업적으로 이용가능하다.* Commercially available from Chemical.
실라놀과 실란디올은 금속 공급원(metal source)과 반응하여 금속 규산염을 수득할 수 있다. 이 금속 공급원(metal source)은 하나 이상의 금속을 포함할 수 있고, 결과물인 금속 규산염은 하나 이상의 금속을 포함할 수 있다. 최소한 어떤 구현예에서 금속 화합물은 실라놀의 약산성 프로톤과 쉽게 반응할 수 있는 것들을 포함한다. 이들 산성 프로톤은 실라놀의 산소에 직접 연결된 것들이다. 산성 프로톤과 반응하는 일반적인 금속 화합물은 대부분의 금속 알킬과 다른 유기 화합물, 금속 알킬아마이드, 임의의 금속 알콕사이드를 포함한다. 모든 특정 화합물의 반응성은 그것을 알콕시실라놀과 섞고 그 혼합물을 핵자기 공명 진단 장치로 분석함으로써 쉽게 증명될 수 있다. 본 발명자들은 물과 반응하는 것으로 알려진 화합물이 알콕시실라놀과도 일반적으로 반응함을 알아내었다.Silanol and silandiol can be reacted with a metal source to yield metal silicates. This metal source may comprise one or more metals, and the resulting metal silicate may comprise one or more metals. In at least some embodiments the metal compounds include those that can readily react with the weakly acidic protons of silanol. These acidic protons are those directly linked to the oxygen of the silanol. Common metal compounds that react with acidic protons include most metal alkyls and other organic compounds, metal alkylamides, and any metal alkoxides. The reactivity of all specific compounds can be easily demonstrated by mixing it with alkoxysilanol and analyzing the mixture with a nuclear magnetic resonance diagnostic device. The inventors have found that compounds known to react with water generally react with alkoxysilanol as well.
상기 반응은 증기 상태에서 진행되고, CVD나 ALD기술을 사용하여 이루어 질 수 있다. 이하에서 보다 자세히 논의되어지는 바와 같이, ALD는 석출 과정의 조절을 제공하고, 넓은 범위의 조건과 다양한 반응물 활성을 갖는 경우의 사용에도 적 합하다.The reaction proceeds in the vapor phase and can be accomplished using CVD or ALD techniques. As discussed in more detail below, ALD provides control of the precipitation process and is also suitable for use with a wide range of conditions and various reactant activities.
규소/금속 비율는 일부 또는 전부의 금속 전구체를 적합한 활성을 갖는 규소 화합물로 치환함으로써 증가시킬 수 있다. 사염화규소(SiCl4)와 같은 규소염화물은, 규소 함량은 증가시키기 위해 사용될 수 있으나, 결과물 안에 불순물로 염소를 남길 수 있고, 그 반응은 소망하는 것보다 느리다. 테트라이소 시아나토실란(tetraisocyanatosilane), 테트라키스(디메틸아미도)실란, 트리스(디메틸아미도)실란과 같은 실리콘 아마이드는 할로겐 오염을 피할 수 있다. 그러나 이들의 석출 속도는 바람직한 경우보다 느리다. 실릴렌(silylene)은 보다 빠르게 반응한다.The silicon / metal ratio can be increased by replacing some or all of the metal precursors with silicon compounds having suitable activity. Silicon chloride, such as silicon tetrachloride (SiCl 4 ), can be used to increase the silicon content, but can leave chlorine as an impurity in the resultant, and the reaction is slower than desired. Silicon amides such as tetraisocyanatosilane, tetrakis (dimethylamido) silane and tris (dimethylamido) silane can avoid halogen contamination. However, their precipitation rate is slower than desired. Silylene reacts faster.
예를 들면, 상기식에서 R은 알킬기이고, 최소한 어떤 구현예에서는 tert-부틸인, 열적으로 안정한 실릴렌7 은 규소/금속의 비율을 증가시키기 위해 금속원의 일부 또는 전체를 대신하여 빠른 반응의 규소원으로 사용될 수 있다.For example, in the above formula, R is an alkyl group, and at least in some embodiments tert -butyl, thermally stable silylene 7 is a fast reacting silicon in place of some or all of the metal sources to increase the silicon / metal ratio. Can be used as a circle.
적어도 어떤 구현예에서는 순수한 이산화 규소가 만들어 질 수 있다. ALD시스템에서 실릴렌이 표면과 반응한 뒤에 충분히 산화되도록 하기 위해 실레인 펄스는 산소 기체 펄스의 뒤를 따르도록 한다. 순수한 이산화 규소는 실릴렌과 산소의 펄스 시퀀스의 반복에 의해 빠르게 석출되어 진다.In at least some embodiments pure silicon dioxide can be made. In an ALD system, the silane pulses follow the oxygen gas pulses to ensure that they are fully oxidized after reacting with the surface. Pure silicon dioxide is rapidly precipitated by repetition of a pulse sequence of silylene and oxygen.
2.금속 인산염과 인 산화물 2.Metal Phosphate and Phosphorus Oxide
본 발명은 금속과 인의 비율이 다양한 금속 인산염을 제조하는 방법을 제공한다. 이 방법은 1이상의 금속 또는 메탈로이드 화합물의 증기와 비스(알킬)포스페이트의 반응을 포함한다. 그 화합물은 기질상에 분말 또는 막을 형성할 수도 있고, 어떤 구현예에서는 가열된 기질위에 형성할 수 있다. 그 화합물은 기질상에 석출되기에 앞서, 비스(알킬)포스페이트의 증기와 금속 또는 메탈로이드 화합물이 혼합됨으로써 기질 위에 형성될 수 있다. 적어도 어떤 구현예에서는 기질은 비스(알킬)포스페이트 증기와 하나 이상의 금속 또는 메탈로이드 화합물에 교대로 노출되어 진다.The present invention provides a process for preparing metal phosphates with varying metal to phosphorus ratios. This method involves the reaction of bis (alkyl) phosphates with the vapor of one or more metal or metalloid compounds. The compound may form a powder or film on the substrate, and in some embodiments may form on a heated substrate. The compound may be formed on the substrate by mixing a metal or metalloid compound with a vapor of bis (alkyl) phosphate prior to precipitation on the substrate. In at least some embodiments, the substrate is exposed to alternating bis (alkyl) phosphate vapors and one or more metal or metalloid compounds.
비스(알킬)포스페이트 반응물은 상업적으로 사용가능하며 종래 또는 알려진 기술을 이용하여 제조될 수 있다. 인 전구체, 디에틸 포스페이트는 Fishier Scientific(Pittsburgh,PA)와 Pfaltz and Bauer(Waterbury,CT)를 포함한 많은 화학 회사로부터 상업적으로 사용가능하다. 디에틸 포스페이트는 염화구리(copper chloride)를 촉매로 하여 에탄올에서 포스피닉산을 공기중 산화시킴으로써 제조될 수 있다.Bis (alkyl) phosphate reactants are commercially available and can be prepared using conventional or known techniques. Phosphorus precursor, diethyl phosphate, is commercially available from many chemical companies including Fishier Scientific (Pittsburgh, PA) and Pfaltz and Bauer (Waterbury, CT). Diethyl phosphate can be prepared by oxidation of phosphonic acid in air in ethanol with copper chloride as a catalyst.
2P(O)OH + 2EtOH + O2 → (EtO)2P(O)OH + 2H2O (4) 2 P (O) OH + 2EtOH + O 2 → (EtO) 2 P (O) OH + 2H 2 O (4)
Y.Okamoto,T.Kusano와 S.Takamuku의 Phosphorous , Sulfur and Silicon , 55권, 195-200페이지 (1991년)에 나타난다. Phosphorous , Sulfur , by Y.Okamoto, T. Kusano and S. Takamuku and See Silicon , Vol . 55, pp. 195-200 (1991).
디이소프로필 포스페이트를 얻기 위한 연쇄반응이 나타나는데, 이소프로판 올의 적절한 치환을 통해 다른 전구체 화합물을 얻는데 사용되어질 수 있다. A chain reaction to obtain diisopropyl phosphate is shown, which can be used to obtain other precursor compounds through appropriate substitution of isopropanol.
PCl3 + 3 iPrOH → (iPrO)2P(O)H + iPrCl+ 2HCl (5)PCl 3 + 3 i PrOH → ( i PrO) 2 P (O) H + i PrCl + 2HCl (5)
(iPrO)2P(O)H + SO2Cl2 → (iPrO)2P(O)Cl + HCl + SO2 (6)( i PrO) 2 P (O) H + SO 2 Cl 2 → ( i PrO) 2 P (O) Cl + HCl + SO 2 (6)
(iPrO)2P(O)Cl + H2O → (iPrO)2P(O)OH + HCl (7)( i PrO) 2 P (O) Cl + H 2 O → ( i PrO) 2 P (O) OH + HCl (7)
McIvor 등의 Canadian J. Chemistry,34권,1825, 1827페이지에 나타난다Appears in Canadian J. Chemistry , McIvor et al., Vol. 34, 1825, 1827.
디이소프로필 포스페이트는 다음 두 반응에 의해 첫번째 형성되는 칼륨염을 이용하여 제조될 수 있다. Diisopropyl phosphate can be prepared using the potassium salt first formed by the following two reactions.
Cl3 + 3 iPrOH → (iPrO)2P(O)H + iPrCl+ 2HCl (8)Cl 3 + 3 i PrOH → ( i PrO) 2 P (O) H + i PrCl + 2HCl (8)
2(iPrO)2P(O)H + KMnO4 + KHCO3 → 2(iPrO)2P(O)OK + MnO2 (9)2 ( i PrO) 2 P (O) H + KMnO 4 + KHCO 3 → 2 ( i PrO) 2 P (O) OK + MnO 2 (9)
A.Zwierak 과 M.Kluba의, Tetrahedron, 27권,3136-3170 페이지에 나타난다.A.Zwierak and M. Kluba, Tetrahedron , Vol. 27, pp. 3136-3170.
다음 두 반응을 통해 나트륨염 유사체를 만들 수 있다.Sodium salt analogues can be made by the following two reactions.
POCl3 + 3iPrOH → (iPrO)3P=O + 3HCl (10)POCl 3 + 3 i PrOH → ( i PrO) 3 P = O + 3HCl (10)
(iPrO)3P=O + NaOH → (iPrO)2P(O)ONa + iPrOH (11)( i PrO) 3 P = O + NaOH → ( i PrO) 2 P (O) ONa + i PrOH (11)
디이소프로필 포스페이트의 전구체는 염산과의 반응을 통해 알칼리염으로부터 자유로워 질 수 있다.The precursor of diisopropyl phosphate can be free from alkali salts through reaction with hydrochloric acid.
(iPrO)2P(O)OM + NaOH → (iPrO)2P(O)OH + MCl, M=Na,K (12)( i PrO) 2 P (O) OM + NaOH → ( i PrO) 2 P (O) OH + MCl, M = Na, K (12)
상기 비스(알킬)포스페이트는 광범위한 범위의 금속 화합물과 반응하여 금속 인산염을 형성한다. 산성 인산 프로톤과 일반적으로 반응하는 금속 화합물은 대부분의 금속 알킬기 및 다른 유기금속 화합물, 금속 알킬아마이드 및 일부 금속 알콕사이드를 포함한다. 특정 화합물의 반응성은 비스(알킬)포스페이트와 그것을 혼합하고 그 혼합물은 핵자기 진동 공명 진단 장치로 분석함으로써 증명될 수 있다.The bis (alkyl) phosphates react with a wide range of metal compounds to form metal phosphates. Metal compounds that generally react with acidic proton phosphate include most metal alkyl groups and other organometallic compounds, metal alkylamides and some metal alkoxides. The reactivity of a particular compound can be demonstrated by mixing it with bis (alkyl) phosphate and analyzing the mixture with a nuclear magnetic vibration resonance diagnostic device.
상기 반응은 증기 상태에서 진행될 수 있으며, CVD 또는 ALD기술을 이용할 수 있을 것이다. 하기 상세히 논의할 바와 같이 ALD는 석출과정을 조절할 수 있고 광범위한 반응 조건과 다양한 반응성을 갖는 반응물에 사용될 수 있다.The reaction can be carried out in the vapor state and may employ CVD or ALD techniques. As discussed in detail below, ALD can control the precipitation process and can be used for reactants having a wide range of reaction conditions and varying reactivity.
인/금속 비율은 적절한 반응성을 갖는 인화합물로 금속 전구체의 일부 또는 전부를 대체함으로써 증가될 수 있다. 포스포러스 트리클로라이드(PCl3), 포스포러스 펜타글로라이드(PCl5), 포스포러스 옥시클로라이드(POCl3)와 같은 인염화물이 사용될 수 있으나 일부 할로겐 불순물이 막에 포함될 수 있다. 헥사메틸 포스포러스 트리아마이드((Me2N)3P), 헥사메틸 포스포리미딕 트리아마이드((Me2N)3P=NH), 헥사메틸 포스포아마이드((Me2N)3PO)와 같은 포스포러스 알킬아마이드는 할로겐 오염을 피할 수 있으나 반응 속도가 느릴 수 있다. 일반적으로 백인 또는 인(Ⅲ)산화물의 도스(dose)는 충분히 산화된 막의 형성을 위해 산소 펄스가 뒤따르게 된다. ALD에 의해 만들어진 인/금속 비율은 인 도스를 물이나 알코올의 도스로 대체함으 로써 감소되어 질 수 있다.The phosphorus / metal ratio can be increased by replacing some or all of the metal precursors with phosphorus compounds with appropriate reactivity. Phosphorus chlorides such as phosphorus trichloride (PCl 3 ), phosphorus pentagloide (PCl 5 ), phosphorus oxychloride (POCl 3 ) may be used but some halogen impurities may be included in the membrane. Hexamethyl phosphorus triamide ((Me 2 N) 3 P), hexamethyl phosphorimide triamide ((Me 2 N) 3 P = NH), hexamethyl phosphoramide ((Me 2 N) 3 PO) Phosphorus alkylamides such as can avoid halogen contamination but may have a slow reaction rate. In general, the dose of white or phosphorus (III) oxide is followed by an oxygen pulse to form a sufficiently oxidized film. The phosphorus / metal ratio produced by ALD can be reduced by replacing phosphorus in water with a dose of water or alcohol.
3.금속 3.Metal 아마이드Amide ,금속 ,metal 알킬Alkyl 및 금속 And metal 알콕사이드Alkoxide
적어도 어떤 구현예에서 금속 또는 메탈로이드 아마이드 화합물은 본 발명의 실시에 있어서 유용하다. 상업적 출처 및/또는 그들의 합성에 관한 참고문헌뿐만 아니라 몇몇의 예들이 표 1에 주어져 있다. 표 1에 언급된 메탈로이드은 붕소,규소,비소이다.In at least some embodiments metal or metalloid amide compounds are useful in the practice of the present invention. Some examples as well as references to commercial sources and / or their synthesis are given in Table 1. Metalloids mentioned in Table 1 are boron, silicon, arsenic.
[표 1] 휘발성 금속 또는 [Table 1] Volatile metals or 메탈로이드Metalloid 아마이드Amide
표 1에서 TMPD는 2,2,6,6-테트라 메틸 피페리다이드(tetramethylpiperidide)를 의미한다. 그 이상의 예들은 1980년에 Ellis Horwood Ltd,a division of JohnWiely&Son에서 발간한 M. F.Lappert,P.P.Power, A.R.Sanger 및TMPD in Table 1 refers to 2,2,6,6-tetramethylpiperidide. Further examples include M. F.Lappert, P.P.Power, A.R.Sanger, published in 1980 by Ellis Horwood Ltd, a division of John Wiley & Son and
R.C.Srivastava의 Metal and Metalloid Amaides에서 발견된다.Found in Metal and Metalloid Amaides, R.C.Srivastava.
적어도 몇몇의 예에서 금속 알킬은 본 발명의 실시에 매우 필요하다. 상업적 출처나 합성에 관한 참고문헌 뿐만 아니라 어떤 예들이 표 2에 주어져 있다.In at least some examples, metal alkyls are very necessary for the practice of the present invention. Some examples are given in Table 2 as well as references to commercial sources or synthesis.
[표 2] 휘발성의 유기금속 화합물[Table 2] Volatile Organometallic Compounds
표 2에서 Cp는 사이클로 펜타디엔의 약자이고, Me5Cp는 펜타메틸 사이클로 펜타디엔을 의미하며, iPrCp은 이소프로필 사이클로 펜타디엔, iPrMe4Cp은 이소프로필 테트라메틸 사이클로 펜타디엔을 의미하고, iPr4Cp은 테트라이소프로필 사이클로 펜타디엔을 의미하며, EtCp는 에틸 사이클로 펜타디엔을, PrCp는 프로필 사이클로 펜타디엔을 ,iPrCp는 이소프로필 사이클로 펜타디엔을 의미하고, BuCp은 부틸사이클로 펜타디엔을, Bz는 벤제나이드를, EtBz은 에틸벤제나이드의 이성질체와 1,5-사이클로 옥타디엔(1,5-COD)의 혼합물을 의미한다.In Table 2, Cp stands for cyclopentadiene, Me 5 Cp means pentamethyl cyclopentadiene, i PrCp means isopropyl cyclopentadiene, i PrMe 4 Cp means isopropyl tetramethyl cyclopentadiene, i Pr 4 Cp stands for tetraisopropyl cyclopentadiene, EtCp stands for ethyl cyclopentadiene, PrCp stands for propyl cyclopentadiene, i PrCp stands for isopropyl cyclopentadiene, BuCp stands for butylcyclo pentadiene , Bz means benzenide, EtBz means a mixture of isomers of ethylbenzenide and 1,5-cyclo octadiene (1,5-COD).
적어도 어떤 구현예에서 금속 또는 메탈로이드 알콕사이드는 본 발명의 시행에 사용될 수 있다. 상업적 출처와 합성의 참고 문헌뿐 아니라 적당한 화합물은 표 3에 주어져 있다.In at least some embodiments a metal or metalloid alkoxide may be used in the practice of the present invention. Suitable compounds as well as commercial sources and synthetic references are given in Table 3.
[표 3] 금속 또는 메탈로이드 Table 3 Metal or Metalloid 알콕사이드Alkoxide
금속염화물 역시 본 발명의 실시에서 사용될 수 있으나, 이들은 일부 할라이드 불순물을 막안에 남기고 기질이나 기구의 부식을 유발하는 단점을 갖고 있다. 4.물이나 알코올과의 반응 Metal chlorides may also be used in the practice of the present invention, but they have the disadvantage of leaving some halide impurities in the film and causing corrosion of the substrate or apparatus. 4.reaction with water or alcohol
적어도 어떤 구현예에서, 금속이 풍부한 규산염과 인산염을 석출해내기 위해 실라놀이나 인산염의 일부를 물로 대체한다. CVD반응기에서 수증기는 기질의 막보다는 증기 입구의 금속 전구체들과 매우 빠르게 반응하는 경향이 있다. ALD반응기에서는 그러한 이른(premature)반응이 일어나지 않는데 이는 반응물이 반응기 안에 있고, 입구에서의 반응이 저지되며, 반응이 기질 표면상에서 한정되어 일어나기 때문이다. 그러나 물은 표면에 강하게 흡수되는 경향이 있어서, 반응물들의 펄스 사이에서 반응기의 불순물을 제거하는데 시간이 많이 걸릴 수 있다.In at least some embodiments, a portion of silanol or phosphate is replaced with water to precipitate out metal rich silicates and phosphates. In CVD reactors, water vapor tends to react very quickly with the metal precursors at the vapor inlet rather than the film of the substrate. Such premature reactions do not occur in ALD reactors because the reactants are in the reactor, the reaction at the inlet is blocked, and the reaction is confined on the substrate surface. However, water tends to be strongly absorbed on the surface, which can take a long time to remove impurities in the reactor between pulses of reactants.
이소프로판올과 tert -부탄올과 같은 알코올은 물이 갖는 이런 문제점을 감소시키는데, 알코올과 금속의 반응이 보다 느리고, 보다 휘발성 있는 알코올이 ALD반응기로부터 보다 빠르게 펌핑될 수 있기 때문이다. 이소프로판올과 tert -부탄올과 같은 알코올은 특별히 열적으로 불안정한(thermally liable) 금속 화합물이 포함되는 반응에 특히 적합하다. 경우에 따라, 알킬 알코올을 분해하여 막으로부터 그 탄소 함량을 제거하기 위하여 기질의 온도를 높인다. 열적으로 불안정한 (thermally liable) 금속 화합물은 보다 높은 기질 온도에서 자가 분해를 할 수 있어서 자기 제한(self-limiting) ALD반응은 일어날 수 없다.Alcohols such as isopropanol and tert - butanol reduce this problem with water because the reaction of alcohol and metal is slower and more volatile alcohol can be pumped out of the ALD reactor faster. Alcohols such as isopropanol and tert - butanol are particularly suitable for reactions involving particularly thermally liable metal compounds. In some cases, the temperature of the substrate is raised to decompose the alkyl alcohol to remove its carbon content from the membrane. Thermally liable metal compounds can self-decompose at higher substrate temperatures so that no self-limiting ALD reaction can occur.
아렌 수화물은 일반적인 알킬 알코올보다 낮은 온도에서 분해되는 알코올의 일종으로서 열적으로 불안정한 금속 화합물이더라도 자가 분해를 피할 수 있는 충분히 낮은 온도에서 탄소가 없는 금속 산화물을 만드는데 사용될 수 있다. 예를 들면 벤젠 수화물은 벤젠 부산물의 방향족의 안정성 때문에 쉽게 물과 벤젠으로 분해된다.Arene hydrate is a type of alcohol that decomposes at lower temperatures than conventional alkyl alcohols and can be used to make carbon-free metal oxides at sufficiently low temperatures to avoid self-decomposition even if they are thermally unstable metal compounds. Benzene hydrates, for example, are easily broken down into water and benzene due to the stability of the aromatics of benzene by-products.
(13) (13)
유용한 다른 아렌 수화물의 예는 다양한 톨루엔 수화물의 이성질체와 같은 알킬 치환 벤젠 수화물들이다.Examples of other arene hydrates that are useful are alkyl substituted benzene hydrates such as isomers of various toluene hydrates.
다른 유용한 알코올은 하기의 두개의 나프탈렌 수화물 및 메틸 나프탈렌 수화물과 같은 알킬 치환 나프탈렌 수화물을 포함한다:Other useful alcohols include alkyl substituted naphthalene hydrates such as the following two naphthalene hydrates and methyl naphthalene hydrates:
따라서 아렌 알코올은 완화된(moderate) 석출 환경에서 금속 화합물의 반응에 사용될 수 있을 것이다. 특히, 여기 기술된 규소와 인산 전구체와 결합되어 사용될 때, 금속 산화물의 형성 또는 금속 규산염 또는 금속 인산염의 형성에 사용될 수 있다. The arene alcohol may thus be used for the reaction of metal compounds in a moderate precipitation environment. In particular, when used in combination with the silicon and phosphoric acid precursors described herein, it can be used for the formation of metal oxides or for the formation of metal silicates or metal phosphates.
적어도 본 발명의 어떤 구현예에서, 금속 아마이드와 물의 반응에서 금속 산화물이 획득된다. 적합한 금속 아마이드는 표 1에 기술된 모든 것을 포함한다.따라서 예를 들자면, 하프늄 산화물은 수증기와 테트라키스(디메틸아미도)하프늄을 사용한 ALD에 의해 제조되었다. 이 ALD반응은 대단히 효율적이고 반응기안으로 운반되는 거의 모든 전구체가 기질위와 반응기의 노출된 벽면에 막으로 석출된다. 또한 반응은 매우 빠르고, 50랭귀뮈어(Langmuirs)미만의 증기 유출(1Langmuir는1초에 10- 6토르의 부분압으로 전구체가 표면으로 운반되는 유출을 의미한다.)에서 완결된다. 반응의 부산물은 디메틸아민 증기를 구성하는 것으로 밝혀졌는데, 이것은 석출된 하프늄 산화물 막을 부식시키지 않는다. 매우 놀랍게도, 테트라키스 하프늄 전구체의 사용은 하프늄 산화물의 매우 균일한 막의 ALD와 매우 높은 종횡비 (aspect ratio(over40))를 갖는 구멍에서조차 성공했다. 하프늄 산화물, HfCl4 및 Hf(O-tert-Bu)4의 ALD의 선행기술에서 흔히 사용된 반응물들은 그렇게 높은 종횡비를 갖는 구멍에서 HfO2의 균일한 석출을 성공시키지 못해왔다. 5.반응물의 증발과 생성물의 석출 In at least some embodiments of the invention, metal oxides are obtained in the reaction of metal amides with water. Suitable metal amides include everything described in Table 1. Thus, for example, hafnium oxide was prepared by ALD using water vapor and tetrakis (dimethylamido) hafnium. This ALD reaction is very efficient and almost all precursors transported into the reactor are deposited on the substrate and on the exposed walls of the reactor. The reaction is very fast, the steam outlet of less than 50 raenggwi Muir (Langmuirs) (1Langmuir from 10 to 1 second, which means that the outflow precursor is transported to the surface in a partial pressure of 6 Torr) is completed at the. The byproduct of the reaction was found to constitute dimethylamine vapor, which does not corrode the deposited hafnium oxide film. Very surprisingly, the use of tetrakis hafnium precursors has been successful even in ALD and very high aspect ratios (over 40) of pores with a very uniform film of hafnium oxide. Hafnium oxide, HfCl 4 And reactants commonly used in the prior art of ALD of Hf (O- tert- Bu) 4 have not been successful in homogeneous precipitation of HfO 2 in such high aspect ratio holes. 5. Evaporation of reactants and precipitation of products
액체 전구체의 증기는 기포기에서의 가열, 박막 증발기를 포함한 전통적인 방법에 의해 형성될 수도 있고, 약100℃에서 25℃로 예열된 운반 기체에 분무되는 방법으로 형성될 수도 있을 것이다. 고체 전구체는 데칸, 도데칸, 테트라데칸, 톨루엔, 크실렌, 메시틸렌, 에테르, 에스테르, 케톤, 염소화된 탄화수소와 같은 탄화수소를 포함하는 유기 용매에 용해되어 질 수 있다. 액체 전구체의 용액은 일반적으로 순수한 용액보다 낮은 점성을 갖기 때문에 어떠한 경우 순수한 액체보다는 용액으로 분무하거나 증발시키는 것이 보다 바람직할 수 있다. 액체나 용액은 또한 박막 증발기나 가열된 부분(heated zone)에 직접 주입함으로써 증발될 수 있다.박막 증발기는 Artisan Industries(Waltham,Massachusetts)에 의해 만들어진 것이다.The vapor of the liquid precursor may be formed by conventional methods, including heating in a bubbler, thin film evaporator, or by spraying a carrier gas preheated from about 100 ° C to 25 ° C. Solid precursors may be dissolved in organic solvents including hydrocarbons such as decane, dodecane, tetradecane, toluene, xylene, mesitylene, ethers, esters, ketones, chlorinated hydrocarbons. Since solutions of liquid precursors generally have a lower viscosity than pure solutions, it may in some cases be more desirable to spray or evaporate into solutions rather than pure liquids. Liquids or solutions can also be evaporated by direct injection into a thin film evaporator or a heated zone. Thin film evaporators were made by Artisan Industries (Waltham, Massachusetts).
액체의 직접적 증발을 위한 상업적 장치는 MKS Instruments(안도버, 메사추세츠), ATMⅠ, Inc.(덴버리, 코네티컷), Novellus Systems,Inc (새너제이, 캘리포니아), COVA Technologies(콜로라도 스프링스. 씨오)에서 만든 것이다. 초음파 분 무기는 Sonotek Corporation(밀톤, 뉴욕)와 Cetac Technologies(오마하, 네브라스카)에 의해 만들어진 것이다.Commercial devices for the direct evaporation of liquids were made by MKS Instruments (Andover, Massachusetts), ATMI, Inc. (Denbury, Connecticut), Novellus Systems, Inc (San Jose, CA), and COVA Technologies (Colorado Springs. . Ultrasonic dust weapons were made by Sonotek Corporation (Milton, New York) and Cetac Technologies (Omaha, Nebraska).
본 발명의 규소 전구체는 표 1에 나타난 금속 또는 메탈로이드 아마이드와 반응하여 금속 규산염이나 메탈로이드 규산염을 형성할 수도 있다. 본 발명의 규소 전구체는 표 2에 나타난 유기금속 화합물과 반응하여 금속 규산염을 형성할 수도 있다. 예를 들면 트리스(tert-부톡시)실라놀은 트리스(tert-부틸(트리메틸실릴)아미도)이트륨(표 1)과 반응하여 이트륨규산염을 형성한다(실시예5,6). 또한, 트리스(tert-부톡시)실라놀은 트리스(tert-부틸(트리메틸실릴)아미도)란탄과 반응하여 란타늄 규산염을 형성한다(실시예7,8). 금속 산화물은 적합한 금속과 물의 반응을 통해서도 얻어진다. 트리스(비스(트리메틸실릴)아미도)란탄은 수증기와 반응하여 보다 란타늄이 풍부한 규산염을 형성한다(실시예21). 란탄늄 산화물은 트리스(2,2,6,6,-테트라메틸 피페리디도)란타늄과 같은 규소가 없는 전구체로부터 석출될 수도 있다(실시예22).The silicon precursor of the present invention may react with the metal or metalloid amide shown in Table 1 to form metal silicate or metalloid silicate. The silicon precursor of the present invention may react with the organometallic compounds shown in Table 2 to form metal silicates. For example tris ( tert -butoxy) silanol reacts with tris ( tert -butyl (trimethylsilyl) amido) yttrium (Table 1) to form yttrium silicates (Examples 5 and 6). In addition, tris ( tert -butoxy) silanol reacts with tris ( tert -butyl (trimethylsilyl) amido) lanthanum to form lanthanum silicates (Examples 7 and 8). Metal oxides are also obtained through the reaction of a suitable metal with water. Tris (bis (trimethylsilyl) amido) lanthanum reacts with water vapor to form more lanthanum-rich silicates (Example 21). Lanthanum oxide may be precipitated from silicon-free precursors such as tris (2,2,6,6, -tetramethyl piperidido) lanthanum (Example 22).
본 발명의 인산염 전구체는 표에 나온 것과 같은 적절한 활성이 있는 금속 화합물과 반응하여 금속 인산염을 형성한다. 예를 들면 디이소프로필 포스페이트는 리튬비스(에틸디메틸실릴)아마이드(표 1)와 반응하여 실시예9,10에서 보여지는 것처럼 리튬이온 전도체인 리튬이온 인산염막을 석출하는 과정에 제공된다.The phosphate precursors of the present invention react with metal compounds with appropriate activity as shown in the table to form metal phosphates. For example, diisopropyl phosphate is provided in the process of reacting with lithium bis (ethyldimethylsilyl) amide (Table 1) to deposit a lithium ion phosphate film which is a lithium ion conductor as shown in Examples 9 and 10.
본 발명의 과정은 화학 증기 석출(CVD)기술 분야에서 잘 알려진 기본적인 장치안에서 진행될 수 있다. CVD기구는 반응물의 증기가 물질이 석출되는 가열된 기질과 접촉하도록 한다. CVD 과정은 보통의 대기압, 또는 낮은 압력을 포함한 다양 한 압력에서 진행될 수 있다. 공업용 대기압 CVD용광로는 Watkins-johnson Company(스콧밸리, 캘리포니아), BTU International(노스 빌러리카, 메사추세츠) Sierratherm(왓슨빌, 캘리포니아)에 의해 미국에서 만들어 졌다. 플로트 생산 라인(float production line)에서의 유리 코팅을 위한 공업용 대기압 CVD기구는 Pilkington North America(톨레도, 오하이오), PPG Industries(피츠버그, 펜실베니아), AFG Industries(킹스포트,테네시)에 의해 미국에서 제작된다. 저기압 CVD기구는 Applied Materials(산타클라라, 캘리포니아), Spire Corporation(베드포드, 메사추세츠), Materials Research Corporation(길버트, 아리조나), NovellusSystems,Inc(새너제이, 캘리포니아), Genus(써니베일, 캘리포니아), Mattson Technology(프리멘트, 씨에이), Emcore Corporation(써머셋, 뉴저지), NZ Applied Technologies(워번, 메사추세츠), COVA Technologies(콜로라도 스프링스,씨오), CVC Corporation(프리몬트, 캘리포니아)에 의해 제작된다.The process of the present invention can be carried out in basic apparatus well known in the chemical vapor deposition (CVD) technique. The CVD apparatus allows the vapor of the reactant to contact the heated substrate from which the material is deposited. The CVD process can be carried out at a variety of pressures, including normal atmospheric pressure or low pressure. Industrial atmospheric CVD furnaces were made in the United States by Watkins-johnson Company (Scott Valley, California) and BTU International (North Billerica, Massachusetts) Sierratherm (Watsonville, California). Industrial atmospheric CVD apparatus for glass coating on float production lines is manufactured in the United States by Pilkington North America (Toledo, Ohio), PPG Industries (Pittsburgh, Pennsylvania), AFG Industries (Kingsport, Tennessee) . Low pressure CVD apparatuses include Applied Materials (Santa Clara, California), Spire Corporation (Bedford, Massachusetts), Materials Research Corporation (Gilbert, Arizona), Novellus Systems, Inc (San Jose, CA), Genus (Sunny Vale, CA), Mattson Technology ( Frement, CA), Emcore Corporation (Someset, New Jersey), NZ Applied Technologies (Woburn, Massachusetts), COVA Technologies (Colorado Springs, Cio), CVC Corporation (Fremont, CA).
원자층 석출(ALD)에 적용되는 기구는 Genus(써니베일, 캘리포니아), ASM Microchemistry(에스푸, 핀란드)로부터 사용가능하다.Apparatuses applied to atomic layer precipitation (ALD) are available from Genus (Sunnyvale, CA), ASM Microchemistry (Espo, Finland).
본 발명의 방법은 또한 원자층(ALD)을 이용하여 수행될 수 있다. ALD는 측정된 양의 제1 반응물 성분의 층석출을 위해 기질을 포함하고 있는 석출기(chamber)에 유입시킨다. 제1 반응물의 박막은 기질위에 석출되어 진다. 소정의 시간이 지난 후, 측정된 양이 제2 반응물 성분이 석출기에 유입되는데, 그곳에서 이미 석출된 제1 반응물 성분의 층위에 석출되고 그 층과 상호작용한다. 제1, 제2 반응물 성분의 교호층을 석출기에 도입하고, 기질상에서 석출되어 조절된 구성과 두께의 층을 형성한다. 석출의 교대는 수초에서 수분이 걸릴 수 있는데, 막 유입된 성분이 기질위에서 충분히 반응하고 기질위의 빈 공간(headspace)로부터 과량의 증기가 제거되기에 적합한 시간이 제공될 수 있도록 채택된 것이다. 표면 반응은 자기 제한적이므로 예상 가능한 조합의 재생 가능한 층이 석출된다는 것이 결정되었다. 두 반응물 성분 이상의 사용은 본 발명의 범위안에 있다.The process of the invention can also be carried out using an atomic layer (ALD). ALD is introduced into a chamber containing a substrate for layer precipitation of the measured amount of the first reactant component. A thin film of the first reactant is deposited on the substrate. After a certain time, the measured amount is introduced into the precipitator, where the second reactant component is deposited on the layer of the first reactant component that has already been precipitated and interacts with the layer. An alternating layer of the first and second reactant components is introduced into the precipitationr and precipitated on the substrate to form a layer of controlled configuration and thickness. The alternating precipitation can take several seconds to a few seconds, so that the membrane-introduced components can be sufficiently reacted on the substrate and provide adequate time for the removal of excess steam from the headspace on the substrate. It has been determined that the surface reaction is self-limiting so that a renewable combination of predictable combinations is deposited. Use of more than two reactant components is within the scope of the present invention.
최소한 본 발명의 어떤 구현예에서, 자동 연료 주입기(Ford model CM-In at least some embodiments of the invention, an automatic fuel injector (Ford model CM-
4722F13Z-9F593-A)는 전구체 용액의 펄스를 질소 운반 기체로 전달하기 위해 사용된다. 용액은 약50 밀리세컨즈 동안 밸브가 열릴때마다 운반되어 진다.4722F13Z-9F593-A) is used to deliver a pulse of precursor solution to the nitrogen carrier gas. The solution is delivered each time the valve is opened for about 50 milliseconds.
본 발명의 다른 구현예에서, 가스 크로마토그래피로 시료를 주입하는데 통상 사용되는 6-포트 샘플링 밸브(Valco modelEP4C6WEPH,Valco Instrument,Houston,TX)는 적당한 운반 기체로 용액의 펄스를 전달하는데 사용되어 질 것이다. 밸브가 열릴 때마다 용액은 튜브안으로 흐르는데, 그 안에서 용액은 튜브 밖을 흐르는 뜨거운 기름으로부터 나온 열에 의해 증발되어 진다. 운반 기체는 증기를 튜브로부터 ALD반응 튜브로 이동시킨다,In another embodiment of the invention, a 6-port sampling valve (Valco model EP4C6WEPH, Valco Instrument, Houston, TX), commonly used to inject a sample by gas chromatography, will be used to deliver a pulse of solution to a suitable carrier gas. . Each time the valve is opened, the solution flows into the tube, where the solution is evaporated by the heat from the hot oil flowing out of the tube. The carrier gas transfers vapor from the tube into the ALD reaction tube,
최소한 어떤 구현예에서 층은 도 1에 도시된 기구를 사용한 ALD에 의해 석출되어 진다. 어떤 구현예에 따르면 측정된 양의 반응물 증기30은 한 쌍의 공기 작용에 의한 칸막이 밸브 50과 70에 의해 가열된 석출기110에 유입되어 진다(Titan Ⅱ모델은 Parker-Hannifin,Richmond CA에 의해 제작). 밸브는 부피V를 갖는 반응기60에 연결되어 있는데, 이 조합은 통제된 온도T2를 갖는 오븐80안에 위치한다. 전 구체 저장고10 안에서의 반응물의 증기압은 이를 둘러싸고 있는 오븐40에 의해 결정된 온도T1에서 고체나 액체 반응물20의 평형 증기압Peq와 동일하다. 온도T1은 전구체 압력Peq가 석출기의 압력Pdep보다 높아질 수 있도록 충분히 높게 선택되어야 한다. 온도T2는 온도T1보다 높게 선택되어지기 때문에 밸브50,70 또는 반응기 60안에서 오로지 증기만 존재하고 응결된 상은 존재하지 않는다. 기체 상태의 반응물의 경우, 전구체 기체 실린더10내의 압력으로부터 압력을 감소시키는 압력 조절기에 의해 그 압력이 결정된다.In at least some embodiments, the layer is deposited by ALD using the apparatus shown in FIG. 1. According to some embodiments, the measured amount of
유사한 조정이 석출기110으로 유입되는 각각의 반응물 전구체에 제공된다.따라서 전구체 저장고 11은 주변 오븐에 의해 유지된 온도T1에서 증기압31을 갖는 고체 또는 액체 반응물21을 담고 있다. 밸브 51과 71은 측정된 부피V를 갖는 반응기61에 연결되어 있고 이 조합은 온도T2인 오븐81안에 존재한다.Similar adjustments are provided to each reactant precursor entering the
운반 기체는 석출기로 들어가는 반응물의 흐름을 가속화하고, 반응 부산물이나 반응하지 않은 증기를 제거하기 위해 통제된 속도로 주입구90으로 흐른다. 가열로(furnace)120에 의해 가열되고 하나 또는 그 이상의 기질130을 담고 있는 석출기110에 들어갈 때, 운반 기체의 전구체 농도를 보다 균일하게 하기 위해서 고정 교반기가 반응기로 들어가는 튜브100에 연결되어 있다. 반응 부산물과 반응하지 않은 증기들은 진공 펌프150을 통과하기 전에 트랩140에 의해 제거되어 진다. 운반 기체는 배출기160으로 나간다.The carrier gas accelerates the flow of reactants into the precipitator and flows to
작동 과정에 있어서, 밸브70은 열리고 그 결과 반응기60의 내부 압력이 석출기110의 내부압력과 근접할 정도로 감소된다. 전구체 저장고10에서 반응기60으로 전구체 증기가 이동하도록 하기 위해 밸브70은 닫히고 밸브50은 열린다. 그리고 나서 밸브50이 닫히고 반응기60의 부피V는 압력Peq에서 전구체 증기를 포함하게 된다. 끝으로, 밸브70이 열리면서 반응기60에 포함된 거의 모든 전구체 증기가 석출기로 들어간게 한다. 이러한 사이클에 의해 운반된 전구체의 몰수, n은 증기가 이상 기체 법칙을 따른다고 가정할 때 예측할 수 있다:In the course of operation, the
n=(Peq- Pdep)(V/RT1) (14)n = (P eq -P dep ) (V / RT 1 ) (14)
상기 R은 기체 상수이다. 이 공식은 또한 튜브90으로부터 나온 운반기체가 짧은 시간동안 전구체 증기를 방출하는 밸브70을 통해 반응기60으로 들어가지는 않는다는 것을 가정한다. 만약 전구체 증기를 포함한 운반 기체의 혼합이 밸브70이 열려 있는 동안 일어나면 보다 많은 양의 전구체 증기가 운반될 것이고, 만약 모든 반응기60의 잔여 전구체 증기가 운반기체로 옮겨 간다면 최대값이 될 것이다.R is a gas constant. This formula also assumes that carrier gas from
n=(Peq)(V/RT1) (15)n = (P eq ) (V / RT 1 ) (15)
상대적으로 높은 증기압을 갖는 전구체에 대해서는(Peq 〉〉Pdep), 전구체 양에 대한 두 측정치의 차이가 없다.For precursors with relatively high vapor pressures (P eq >> P dep ), there is no difference between the two measurements of precursor amount.
요구되는 전구체20의 양이 반응기로 전달되기 전까지, 필요하다면 전구체20의 운반 사이클은 반복되어 진다. 보통,ALD 과정에서 이 사이클에 의해 전달되는 전구체20의 양은 표면 반응을 완결("포화"라고도 함)시킬 만큼 충분히 많이 선택되 어 진다.The transfer cycle of
제2 전구체21로부터 나온 다음 단계의 증기31은, 제1 전구체20을 위한기구들과 유사하게 순서 매겨진 요소들을 갖는 비슷한 기구에 의해 측정되고 운반될 것이다.The next stage of
Pdep보다 낮은 Peq를 갖는 전구체의 경우, 이 방법으로는 어떤 전구체도 석출기로 운반할 수 없을 것이다. 온도T1을 올림으로써 증기압은 증가될 수 있으나 고온의 경우 전구체의 열분해를 일으킬 수 있다. 낮은 증기압을 갖고 열에 민감한 전구체의 경우, 증기는 도 3에 나타난 기구를 이용하여 운반 되어질 것이다. 반응기220은 먼저 압력 조절기로부터 튜브240과 밸브220을 통해 운반된 운반 기체로 채워진다. 이후에 밸브220은 닫히고 밸브210이 열리면서, 운반 기체는 전구체 저장고220의 압력이 Ptot가 되도록 충전시킨다. 그러면 저장고10의 증기 공간 30(vapor space)의 전구체의 몰분율은 Peq/Ptot이다. 만약Ptot가 석출기의 압력Pdep보다 큰 압력으로 고정된다면 한번에 운반되는 몰수는 다음 방정식에 의해 예측된다.In the case of precursors with P eq lower than P dep , this method will not transport any precursor to the precipitator. Increasing the temperature T 1 can increase the vapor pressure, but at high temperatures can cause pyrolysis of the precursor. In the case of low vapor pressure and heat sensitive precursors, the vapor will be transported using the apparatus shown in FIG.
n=(Peq/Ptot)(Ptot- Pdep)(V/RT1) (16)n = (P eq / P tot ) (P tot -P dep ) (V / RT 1 ) (16)
상기 V는 반응기10의 증기 공간 30의 부피이다. 이 양은 밸브230을 여는 것으로써 운반된다. 만약 튜브90에서 나온 기체가 밸브230이 열려 있는 시간 동안 증기 공간 30으로 들어간다면 이 예측치보다 많은 양이 운반될 수가 있을 것이다. 부피V를 충분히 확장함으로써 표면 반응을 충분히 일어날 수 있도록 하는 양의 전 구체가 운반될 수 있을 것이다. 만약 증기압Peq가 너무 낮아서 주어진 공간V가 비현실적으로 크다면 다른 반응물이 운반되기 이전에 공간V로부터 추가적인 양이 운반될 수도 있을 것이다.V is the volume of the
비슷한 기구가 본 시스템의 각각의 전구체 반응물에도 적용된다. 따라서 반응기221은 먼저 압력 조절기로부터 튜브241과 밸브201을 통해 전달된 운반 기체에 의해 채워진다. 그런 다음 밸브201은 닫히고 밸브211이 열리면서 운반 기체가 전구체 저장고11의 압력이 Ptot가 되도록 채운다. 밸브231을 여는 것으로써 이 양이 운반된다. 튜브91로부터 나온 운반 기체는 측정된 양의 석출기로의 운반을 촉진한다. 일반적으로 등온의 석출기에서 물질은 기질과 반응기 내부의 벽 등, 전구체 증기에 노출된 모든 표면에서 석출된다. 따라서 기질과 노출된 반응기 벽면의 단위면적당 사용되는 전구체의 몰양을 조사하는 것이 적합하다.Similar mechanisms apply to each precursor reactant in the system. Thus, the
여기에 나타난 액체나 용액은 분사 코팅, 스핀 코팅, 혼합 금속 산화물의 졸-겔 형성과 같은 다른 종류의 석출 과정에서도 금속을 포함하는 전구체로 사용되어 질 수 있을 것이다. 이러한 전구체의 높은 용해도와 혼화성은 필요한 용액 형성에 있어 한 장점이 된다.The liquids or solutions shown here may be used as precursors containing metals in other types of precipitation processes such as spray coating, spin coating, and sol-gel formation of mixed metal oxides. The high solubility and miscibility of these precursors is an advantage in forming the required solution.
이들 예에 포함된 아마이드는 미국 수송부(USDT)에서 발표한 방법에 따르면 불연성인 것으로 나타난다. 불연성의 다공성 고체위에 약 5밀리리터의 물질을 떨어뜨리고 자발적인 연소 반응이 일어나는지를 관찰하는 실험이 필요하다. 와트만 No.3거름 종이에 5밀리리터의 액체나 용액을 떨어뜨리고 어떤 불꽃이나 숯같은 것 이 발생하는 지를 관찰하는 실험도 포함된다.Amides included in these examples appear to be nonflammable according to methods published by the US Department of Transportation (USDT). An experiment is needed to drop about 5 milliliters of material onto a non-combustible porous solid and observe if a spontaneous combustion reaction occurs. Experiments include dropping 5 milliliters of liquid or solution onto Whatman 3 paper and observing what kind of flame or charcoal is occurring.
일반적으로 전구체는 주위 공기중의 습기와 반응하므로 순수한 질소 기체와 같은 불활성의 건조한 기체 속에 보관되어야 한다.In general, precursors react with moisture in the ambient air and therefore must be stored in an inert, dry gas such as pure nitrogen gas.
[실시예]EXAMPLE
본 발명은, 청구 범위에 기술된 범위를 제한하지 않고 단지 설명을 위한 목적으로 첨부된 이하의 예들을 참고하여 이해될 수 있을 것이다.The invention will be understood with reference to the following examples, which are appended for illustrative purposes only, without limiting the scope described in the claims.
실시예1Example 1 : 지르코늄 규산염의 Of zirconium silicate CVDCVD
메시틸렌에 트리스(tert-부틸)실라놀(1%w)을 혼합한 용액이 질소 기체가 0.4L/min으로 통과하는 1/16"O.D.지점을 향해 6ml/hour로 펌핑된다. 그 결과물인 흰 연기가 250℃로 가열된 튜브로 흐른다. 메시틸렌에 테트라키스(에틸메틸아미도)지르코늄(1%w)을 혼합한 용액이 질소 기체가 0.4L/min으로 통과하는 1/16"O.D.지점으로 12ml/hour속도로 펌핑된다. 그 결과물인 흰 연기가 위와 같은 튜브로 흐른다.기체압력은 액체 질소 트랩 옆에 위치한 유리관 배출구에 연결된 진공 펌프를 이용하여 5토르(Torr)로 유지시킨다. 튜브안의 규소 기질과 유리질의 탄소는, 튜브 길이에 따라 두께가 다양한 지르코늄 규산염의 막으로 코팅되어 진다. 러더포드 후광 산란 분광기(Rutherford backscattering spectroscopy)에 의한 막 분석은 유리질 탄소에 ZrSi2O6막이 석출되었음을 보여 준다. 막에서 탄소와 질소성분은 검출되지 않는다. 규소 위에 석출된 막의 굴절율은 타원편광반사법에 의하면 약1.6이 되는 것으로 나타난다. 실시예2 : 지르코늄 규산염의 ALD A solution of tris ( tert -butyl) silanol (1% w) mixed with mesitylene is pumped at 6ml / hour towards the 1/16 "OD point where nitrogen gas passes at 0.4L / min. Smoke flows into a tube heated to 250 ° C. A solution of tetrakis (ethylmethylamido) zirconium (1% w) mixed with mesitylene to a 1/16 ”OD point where nitrogen gas passes at 0.4 L / min. Pumped at 12ml / hour The resulting white smoke flows into the tube as above; the gas pressure is maintained at 5 Torr using a vacuum pump connected to the glass tube outlet located next to the liquid nitrogen trap. The silicon substrate and the glassy carbon in the tube are coated with a film of zirconium silicate that varies in thickness depending on the tube length. Membrane analysis by Rutherford backscattering spectroscopy showed that a ZrSi 2 O 6 film was deposited on the glassy carbon. Carbon and nitrogen are not detected in the film. The refractive index of the film deposited on silicon appears to be about 1.6 according to the elliptical polarization reflection method. Example 2 ALD of Zirconium Silicate
전구체가 연속적인 대신에 5초 간격의 변형된 펄스로 주입되는 것을 제외하고는 실시예1이 반복되어 진다. 비슷한 구성의 막( ZrSi2O6)이 가열된 전체 길이를 따라 균일한 두께로 석출된다. 그 두께는 한 사이클당 약 0.3nm이다. Example 1 is repeated except that precursors are injected in modified pulses at 5 second intervals instead of continuous. A similarly constructed film (ZrSi 2 O 6 ) is deposited to a uniform thickness along the entire heated length. The thickness is about 0.3 nm per cycle.
실시예3Example 3 : 하프늄 규산염의 : Of hafnium silicate CVDCVD
테트라키스(에틸메틸아미도)지르코늄 대신에 테트라키스(에틸메틸아미도)하프늄이 사용되는 것을 제외하고는 실시예1이 반복된다. 막은 HfSi2O6에 근접하는 구조인 것으로 밝혀졌다. 막에서 어떤 탄소나 질소는 검출되지 않는다. 규소위에 석출된 막의 굴절율은 타원편광 반사법에 의하면 약1.6이 되는 것으로 나타난다.Example 1 is repeated except that tetrakis (ethylmethylamido) hafnium is used instead of tetrakis (ethylmethylamido) zirconium. The film was found to have a structure close to HfSi 2 O 6 . No carbon or nitrogen is detected in the membrane. The refractive index of the film deposited on silicon appears to be about 1.6 according to the elliptical polarization reflection method.
실시예4Example 4 : 하프늄 규산염의 : Of hafnium silicate ARDARD
전구체가 연속적인 대신에 5초 간격의 변형된 펄스로 주입되는 것을 제외하고는 실시예3이 반복되어 진다. 비슷한 구성의 막(HfSi2O6)이 가열된 전체 길이를 따라 균일한 두께로 석출된다. 그 두께는 한 사이클당 약 0.3nm이다. Example 3 is repeated except that precursors are injected in modified pulses at 5 second intervals instead of continuous. A similarly constructed film (HfSi 2 O 6 ) is deposited to a uniform thickness along the entire heated length. The thickness is about 0.3 nm per cycle.
실시예5Example 5 : 이트륨 규산염의 Of yttrium silicate CVDCVD
테트라키스(에틸메틸아미도)지르코늄 대신에 트리스(tert-부틸(트리메틸실릴)아미도)이트륨이 사용되는 것을 제외하고는 실시예1이 반복된다. 막은 Y2Si2O7에 근접하는 구조인 것으로 밝혀졌다. 막에서 어떤 탄소나 질소는 검출되지 않는 다. 규소 위에 석출된 막의 굴절율은 타원편광 반사법에 의하면 약1.6이 되는 것으로 나타난다.Example 1 is repeated except that tris ( tert -butyl (trimethylsilyl) amido) ylium is used in place of tetrakis (ethylmethylamido) zirconium. The film was found to have a structure close to Y 2 Si 2 O 7 . No carbon or nitrogen is detected in the membrane. The refractive index of the film deposited on silicon appears to be about 1.6 according to the elliptical polarization reflection method.
실시예6Example 6 : 이트륨 규산염의 Of yttrium silicate ARDARD
전구체가 연속적인 대신에 5초 간격의 변형된 펄스로 주입되는 것을 제외하고는 실시예5가 반복되어 진다. 한 구성의 막(Y2Si2O7)이 가열된 전체 길이를 따라 균일한 두께로 석출된다. 두께는 한 사이클당 약 0.3nm이다.Example 5 is repeated except that precursors are injected in modified pulses at 5 second intervals instead of continuous. A film Y 2 Si 2 O 7 of one configuration is deposited to a uniform thickness along the entire heated length. The thickness is about 0.3 nm per cycle.
실시예7Example 7 : : 란탄늄Lanthanum 규산염의 Silicate CVDCVD
테트라키스(에틸메틸아미도)지르코늄 대신에 트리스(비스(트리메틸실릴)아미도)란탄늄이 사용되는 것을 제외하고는 실시예1이 반복된다. 약 0.9의 La:Si비율을 갖는 막이 기질 온도 250℃에서 유리질의 탄소 기질위에 형성된다. 막에서 어떤 탄소나 질소성분은 검출되지 않는다.Example 1 is repeated except that tris (bis (trimethylsilyl) amido) lantanium is used instead of tetrakis (ethylmethylamido) zirconium. A film having a La: Si ratio of about 0.9 is formed on the glassy carbon substrate at a substrate temperature of 250 ° C. No carbon or nitrogen content is detected in the film.
실시예8Example 8 : : 란탄늄Lanthanum 규산염의 Silicate ARDARD
전구체가 연속적인 대신에 5초 간격의 변형된 펄스로 주입되는 것을 제외하고는 실시예7이 반복되어 진다. 비슷한 구성의 막이 가열된 전체 길이를 따라 균일한 두께로 석출된다.Example 7 is repeated except that the precursors are injected in modified pulses at 5 second intervals instead of continuous. A film of similar construction is deposited to a uniform thickness along the entire length of the heating.
실시예9Example 9 : 리튬 인산염의 : Of lithium phosphate CVDCVD
액체 리튬비스(에틸디메틸실릴)아마이드(1%w)이 메시틸렌과 혼합되어 진다. 그 결과물인 용액은, 질소 기체가 250℃로 가열된 관로의 석출 위치를 향해 0.30L/min속도로 흐르는 지점으로 12ml/hour로 펌핑됨으로써 분무되어 진다. 동시 에 1%의 디이소프로필 포스페이트의 메시틸렌 용액은 같은 관로(tube furnace)로 0.30 L/min속도로 흐르는 다른 질소 운반 기체로 분무된다. 기체 압력은 액체 질소 트랩 옆에 위치한 유리관 배출구에 연결된 진공 펌프를 이용하여 5토르(Torr)로 유지시킨다. 튜브 안 뿐만 아니라 유리 튜브 바닥의 규소 기질 위에도 박막이 석출된다. 그 두께 분석표는 관로(tube furnace)로 들어가는 기체의 입구 근처에서 최고점을 나타낸다. X-ray광전자 분광기를 이용한 분석에 의하면 막은 리튬, 인산 및 산소를 포함한다.Liquid lithium bis (ethyldimethylsilyl) amide (1% w) is mixed with mesitylene. The resulting solution is sprayed by pumping at 12 ml / hour to the point where nitrogen gas flows at a rate of 0.30 L / min towards the precipitation location of the conduit heated to 250 ° C. Simultaneously, a 1% mesitylene solution of diisopropyl phosphate is sprayed into another nitrogen carrier gas flowing at a rate of 0.30 L / min in the same tube furnace. The gas pressure is maintained at 5 Torr using a vacuum pump connected to the glass tube outlet located next to the liquid nitrogen trap. A thin film is deposited not only in the tube but also on the silicon substrate at the bottom of the glass tube. The thickness table shows the peak near the gas inlet entering the tube furnace. Analysis using X-ray photoelectron spectroscopy shows that the membrane contains lithium, phosphoric acid and oxygen.
실시예10Example 10 : 리튬 인산염의 : Of lithium phosphate ALDALD
전구체가 연속적인 대신에 5초 간격의 변형된 펄스로 주입되는 것을 제외하고는 실시예9가 반복되어 진다. 석출 지역 전체를 통해 거의 일정한 두께라는 것을 제외하면 비슷한 리튬 인산염 막이 석출된다.Example 9 is repeated except that precursors are injected in modified pulses at 5 second intervals instead of continuous. A similar lithium phosphate film is deposited throughout the deposition area, except for a nearly constant thickness.
비교예1Comparative Example 1 : : 트리스(Tris tert-tert- 부톡시)실라놀만을Butoxy) silanol only 이용한 제한 Limit 석출Precipitation
단지 규소 전구체만을 사용하고 지르코늄을 사용하지 않는다는 것을 제외하고는 실시예1이 반복된다. 어떤 막도 석출되지 않는다.Example 1 is repeated except that only silicon precursor is used and no zirconium is used. No membrane is precipitated.
비교예2Comparative Example 2 : : 테트라키스(에틸메틸아미도)지르코늄만을Only tetrakis (ethylmethyl amido) zirconium 이용한 제한 Limit 석출Precipitation
단지 지르코늄 전구체만을 사용하고 규소 전구체를 사용하지 않는다는 것을 제외하면 실시예1이 반복된다. 어떤 막도 석출되지 않는다.Example 1 is repeated except that only a zirconium precursor is used and no silicon precursor is used. No membrane is precipitated.
비교예3Comparative Example 3 : : 테트라키스(에틸메틸아미도)하프늄만을Only tetrakis (ethylmethyl amido) hafnium 이용한 제한 Limit 석출Precipitation
단지 하프늄 전구체만을 사용하고 규소 전구체를 사용하지 않는다는 것을 제외하면 실시예3이 반복된다. 어떤 막도 석출되지 않는다.Example 3 is repeated except that only hafnium precursor is used and no silicon precursor is used. No membrane is precipitated.
비교예4Comparative Example 4 : 트리스(Tris terttert -- 부틸(트리메틸실릴)아미도Butyl (trimethylsilyl) amido )이트륨만을 이용한 제한 Restriction using only yttrium 석출Precipitation
단지 이트륨 전구체만을 사용하고 규소 전구체를 사용하지 않는다는 것을 제외하면 실시예5가 반복된다. 어떤 막도 석출되지 않는다.Example 5 is repeated except that only yttrium precursor is used and no silicon precursor is used. No membrane is precipitated.
비교예5Comparative Example 5 : 트리스(Tris 비스(트리메틸실릴)아미도Bis (trimethylsilyl) amido )란탄늄만을 이용한 제한 Restriction using only lanthanum 석출Precipitation
단지 란탄늄 전구체만을 사용하고 규소 전구체를 사용하지 않는다는 것을 제외하면 실시예7이 반복된다. 어떤 막도 석출되지 않는다.Example 7 is repeated except that only lanthanum precursor is used and no silicon precursor is used. No membrane is precipitated.
비교예6Comparative Example 6 : : 디이소프로필포스페이트만을Only diisopropyl phosphate 이용한 제한 Limit 석출Precipitation
단지 인산 전구체만을 사용하고 리튬 전구체를 사용하지 않는다는 것을 제외하면 실시예9가 반복된다. 어떤 막도 석출되지 않는다.Example 9 is repeated except that only a phosphoric acid precursor is used and no lithium precursor is used. No membrane is precipitated.
비교예7Comparative Example 7 : : 리튬비스(에틸메틸실릴)아마이드만을Lithium bis (ethylmethylsilyl) amide only 이용한 제한 Limit 석출Precipitation
*단지 리튬 전구체만을 사용하고 인산 전구체를 사용하지 않는다는 것을 제외하면 실시예9가 반복된다. 어떤 막도 석출되지 않는다.Example 9 is repeated except that only a lithium precursor is used and no phosphoric acid precursor is used. No membrane is precipitated.
실시예11Example 11 : : 금속규산연과Metal silicate lead 인산염의 Phosphate ALDALD 형성 formation
전구체 용액의 펄스를 질소 운반 기체로 운반하는 자동 연료 주입기(Ford model F13Z-9F593-A)를 사용하여 실시예2, 4, 6, 8, 10의 ALD를 반복한다. 약 50ms동안 밸브가 열릴 때마다 0.05m의 용액이 운반되어 진다. 비슷한 결과들이 얻어진다.The ALDs of Examples 2, 4, 6, 8, and 10 are repeated using an automatic fuel injector (Ford model F13Z-9F593-A) carrying a pulse of precursor solution to a nitrogen carrier gas. Each time the valve is opened for about 50 ms, 0.05 m of solution is delivered. Similar results are obtained.
테트라데칸 용액의 펄스를 질소기체로 운반하기 위해, 보통 기체 크로마토그 래피에서 시료를 주입하는데 사용되는 6-port 샘플링 밸브를 사용하여 예2, 4, 6, 8, 10의 ALD를 반복한다. 50㎕의 부피를 갖는 외부시료 루프들이 사용되었다. 밸브가 열릴때마다, 튜브 밖을 흐르는 뜨거운 기름으로부터 나온 열에 의해 용액이 증발되는 곳인 1/16"O.D., 0.040"I.D.니켈 튜브에, 약 50㎕의 용액이 흘러 들어간다. 질소 운반 기체는 증기를 작은 튜브로부터 ALD반응 튜브로 이동시킨다. 비슷한 결과들이 얻어진다.To deliver pulses of tetradecane solution to the nitrogen gas, repeat the ALDs of Examples 2, 4, 6, 8, and 10 using the 6-port sampling valve normally used to inject the sample in gas chromatography. External sample loops with a volume of 50 μl were used. Each time the valve is opened, approximately 50 μl of solution flows into a 1/16 "O.D., 0.040" I.D. nickel tube, where the solution is evaporated by heat from the hot oil flowing out of the tube. Nitrogen carrier gas transports vapor from the small tube into the ALD reaction tube. Similar results are obtained.
다른 일련의 예에서는, ALD실험을 위해 상온에서 액체인 전구체들의 펄스가, 작은(0.5㎕) 내부 샘플링 루프(Valco model EH2CI4WE.5PH,ValcoIn another series of examples, the pulses of precursors that are liquid at room temperature for ALD experiments are small (0.5 μl) internal sampling loop (Valco model EH2CI4WE.5PH,
Instruments,Houston,TX))를 갖는 4-port 샘플링 밸브를 사용하여 예2,4,6,8,10와 유사하게 운반되어 진다. 밸브가 열릴때마다, 튜브 밖을 흐르는 뜨거운 기름으로부터 나온 열에 의해 용액이 증발되는 곳인 1/16"O.D.,0.040"I.D.니켈 튜브에, 약 50㎕의 용액이 흘러 들어간다. 질소 운반 기체는 증기를 작은 튜브로부터 ALD반응 튜브로 이동시킨다. 비슷한 결과들이 얻어진다.Using a 4-port sampling valve with Instruments, Houston, TX), it is transported similarly to Examples 2, 4, 6, 8, and 10. Each time the valve is opened, approximately 50 μl of solution flows into a 1/16 "O.D., 0.040" I.D. nickel tube, where the solution is evaporated by heat from the hot oil flowing out of the tube. Nitrogen carrier gas transports vapor from the small tube into the ALD reaction tube. Similar results are obtained.
실시예12Example 12 : 하프늄 산화물의 : Of hafnium oxide ALDALD
도 1의 기구를 이용하여 하프늄 산화물 층이 석출된다. 0.5×10-9moles/cm2의테트라키스(디메틸아미도)하프늄 증기와 4 ×10-9moles/cm2의 수증기가 250℃의 석출기로 5초마다 교대로 주입되어 진다. 또한 석출기에는 0.15토르의 압력이 유지되도록, 충분한 질소 기체가 연속적으로 흐르도록 한다. 석출기는 기체가 흐르는 방향에 대해 수직으로 2.3cm2의 단면적을 갖는다. 석출기의 배출구는 약0.012초 만에 석출기의 부피와 동일한 부피를 펌핑해낼 수 있는 충분한 용량의 진공 펌프에 연결되어 있다.A hafnium oxide layer is deposited using the mechanism of FIG. Tetrakis (dimethyl amido) hafnium vapor of 0.5 × 10 −9 moles / cm 2 and water vapor of 4 × 10 −9 moles / cm 2 are alternately injected every 5 seconds into a 250 ° C precipitater. In addition, sufficient nitrogen gas is continuously flowed through the precipitator so that a pressure of 0.15 Torr is maintained. The precipitator has a cross-sectional area of 2.3 cm 2 perpendicular to the direction in which the gas flows. The outlet of the precipitator is connected to a vacuum pump of sufficient capacity to pump a volume equal to the volume of the precipitator in about 0.012 seconds.
이러한 반응 환경의 결과, 투명하고 절연성의 하프늄 산화물 막이 석출기와 그 내부 벽에 있는 기질위에 석출되어 진다. 그 구조는 유리질의 탄소 기질위의 막에 대한 러더포드 후방산란 분광기(RBS)의 분석에 의해 HfO2인 것으로 결정되었다. 어떠한 탄소와 질소 성분도 검출되지 않는다. 타원편광 반사 방법에 의하면 그 두께는 0.1nm/cycle이고 굴절률은 2.03이다. RBS결과와 타원편광 반사 방법의 결과를 조합하면 약 9의 밀도가 얻어진다. 두께는 모든 석출 영역 전체에 대해 오차 범위 1%이내에서 일정하다. small-angle X-ray반사계수 측정은 두께를 확인시켜 주었고, 밀도를 9.23g/cm2으로 알려 주었다. 또한 X-ray반사계수는 막이 매우 부드러워서 43nm의 두께의 막에 대해 0.4nm의 조면도를 갖는다는 것을 보여준다. 전자 현미경의 스캐닝은 150℃에서 생성된 막이 250℃의 경우보다 부드러움을 알 수 있다.As a result of this reaction environment, a transparent and insulating hafnium oxide film is deposited on the precipitater and the substrate on its inner wall. The structure was determined to be HfO 2 by analysis of Rutherford Backscatter Spectroscopy (RBS) on a film on a glassy carbon substrate. No carbon and nitrogen components are detected. According to the elliptical polarization reflection method, the thickness is 0.1 nm / cycle and the refractive index is 2.03. Combining the results of the RBS result with the elliptical polarization reflection method, a density of about 9 is obtained. The thickness is constant within an error range of 1% for all precipitation regions as a whole. Small-angle X-ray reflection coefficient measurements confirmed the thickness and gave a density of 9.23 g / cm 2 . The X-ray reflection coefficient also shows that the film is very soft and has a roughness of 0.4 nm for a 43 nm thick film. Scanning of the electron microscope reveals that the film produced at 150 ° C. is softer than at 250 ° C.
더 많은 양의 반응물로 실시예12를 반복하면, 막의 두께는 증가하지 않고,그 함량만 변한다. 이러한 결과는 표면 반응이 자기 제한적임(self-limiting)을 의미한다. 이 결론은 석출기110 안에 석영 결정 마이크로 밸런스를 넣음으로써 확인되는데, 반응물의 양이 증가할 때, 초기에는 석출된 양이 증가하다가 나중에는 그 상승이 멈춘다는 것이다. 이러한 자기 제한적인 표면 반응의 결과에 따르면 직경에 대한 길이의 비가 50인 구멍안에서도 균일한 막이 형성될 수 있다. 이러한 구멍안 의 두께의 균일성은, 구멍이 없는 평평한 표면에서 포화 반응이 일어나는데 필요한 최소한의 양의 10배까지 반응물의 양을 증가시킴으로써, 증진시킬 수 있다. 진공 펌프의 용량을 감소시키는 것 또한 석출기를 통과하는 증기의 선형계수를 감소시킴으로써 단계적인 피복률을 증진시킬 수 있고, 그것 때문에 증기가 구멍에까지 확산하는데 걸리는 시간, 즉, 유량(flux)이 증가한다. 도 3은 하프늄 산화물로 코팅된 구멍들의 현미경 사진을 스캐닝한 것이데, 고도로 균일한 두께를 보여준다. 하프늄 산화물층은, 규소안의 어두운 배경으로 나타나는 좁은 수직의 구멍 각각에 대해, 밝은 테두리를 이루고 있다. 현미경 사진의 꼭대기에는, 하프늄 산화물의 석출에 앞서 구멍이 부식되기 시작하는 부분인 규소의 윗면(upper surface)이 나타난다.Repeating Example 12 with a higher amount of reactant does not increase the thickness of the membrane, only its content changes. This result means that the surface response is self-limiting. This conclusion is confirmed by putting the quartz crystal microbalance in the
기질 온도100℃- 300℃의 범위에서 실시예12를 반복하면 비슷한 결과가 나온다. 300℃이상의 온도에서 테트라키스(디메틸아미도)하프늄의 양을 증가시킴에 따라 두께가 증가한다. 이것은 표면 반응이, 300℃이상의 온도에서는 테트라키스(디메틸아미도)하프늄의 열분해때문에, 자기 제한이 아니라는 것을 보여 준다.Repeating Example 12 in the substrate temperature range of 100 ° C.-300 ° C. yields similar results. The thickness increases with increasing amounts of tetrakis (dimethylamido) hafnium at temperatures above 300 ° C. This shows that the surface reaction is not self limiting due to the thermal decomposition of tetrakis (dimethyl amido) hafnium at temperatures above 300 ° C.
실시예13Example 13 : 지르코늄 산화물의 Of zirconium oxide ALDALD
테트라키스(디메틸아미도)하프늄 대신에 테트라키스(디메틸아미도)지르코늄을 이용하여 실시예12를 반복한다. 비슷한 성질을 갖는 지르코늄 산화물의 막이 석출된다.Example 12 is repeated using tetrakis (dimethylamido) zirconium instead of tetrakis (dimethylamido) hafnium. A film of zirconium oxide having similar properties is deposited.
실시예14Example 14 : 하프늄 산화물의 : Of hafnium oxide ALDALD
수증기 대신에 tert-부탄올 증기를 이용하여 실시예12를 반복한다. 비슷한 성질을 갖는 하프늄 산화물의 막이 석출된다.Example 12 is repeated using tert -butanol vapor instead of water vapor. A film of hafnium oxide having similar properties is deposited.
실시예15 : 탄탈륨 산화물의 ALD Room 15 o'clock: ALD of tantalum oxide
테트라키스(디메틸아미도)하프늄 증기 대신에 에틸이미도트리스(디에틸아미도)탄탈륨 증기를 이용하여 실시예12를 반복한다. Ta2O5의 투명한 막이 석출된다. 이들은 굴절률2.2를 갖고, 한 사이클마다 약0.06의 두께를 갖는다.Example 12 is repeated using ethylimidotris (diethylamido) tantalum vapor instead of tetrakis (dimethylamido) hafnium vapor. A transparent film of Ta 2 O 5 precipitates. They have a refractive index of 2.2 and a thickness of about 0.06 per cycle.
실시예16Example 16 : 알루미늄 인산염의 : Of Aluminum Phosphate ALDALD
3×10-9moles/cm2양의 트리메틸알루미늄 증기와 디이소프로필포스페이트를 기질 온도 400℃에서 교대로 이용하여 ALD를 실시한다. 구조식Al2P4O13을 갖는 투명한 알루미늄 포스페이트 막이 사이클마다 0.1nm의 속도로 석출된다. 이들은 약 1.5의 굴절율을 갖는다.ALD is carried out using alternating trimethylaluminum vapor and diisopropylphosphate in an amount of 3 × 10 −9 moles / cm 2 at a substrate temperature of 400 ° C. A transparent aluminum phosphate film having the structural formula Al 2 P 4 O 13 precipitates at a rate of 0.1 nm per cycle. They have a refractive index of about 1.5.
실시예17Example 17 : 알루미늄 규산염의 : Of aluminum silicate ALDALD
기질 온도 300℃에서 3×10-9moles/cm2양의 트리메틸알루미늄 증기와 1.2×10-8moles/cm2양의 트리스(tert-butoxy)실라놀 증기를 교대로 이용하여 ALD를 실시한다. 구조식Al2Si8O19을 갖는 투명한 알루미늄 규산염 막이 사이클마다 1nm의 놀랄만큼 빠른 속도로 석출된다. 이들은 약 1.48의 굴절율을 갖는다. 막의 표면은 매우 매끄럽다; 원자 현미경은 150nm의 알루미늄 규산염 두께에 대해 0.8nm이하의 제곱 평균 조면도를 갖는다는 사실을 보여 준다. 규소 기질상의 2㎛두께의 막에서 장력은 약0.2giga-Pascal로 측정되었다. 단일 결정 규소위에서 석출된 막은 보다 작은 장력인 0.03giga-Pascal을 나타내었다. 6미크론 두께의 막은 장력때문에 금(crack)과 갈라짐(delamination)을 보였다.In the substrate temperature 300 ℃ 3 × 10 -9 moles / cm 2 amounts of trimethyl aluminum vapor and 1.2 × 10 -8 moles / cm 2 amounts of tris (tert- butoxy) performs the ALD using a silanol steam alternately. A transparent aluminum silicate film having the structure Al 2 Si 8 O 19 precipitates at a surprisingly fast rate of 1 nm per cycle. They have a refractive index of about 1.48. The surface of the membrane is very smooth; Atomic microscopy shows that it has a root mean roughness of less than 0.8 nm for an aluminum silicate thickness of 150 nm. The tension was measured to be about 0.2 giga-Pascal in a 2 μm thick film on a silicon substrate. The film deposited on the single crystal silicon had a smaller tension of 0.03giga-Pascal. The 6 micron thick membrane showed cracking and delamination due to tension.
이러한 장력은 플라즈마 처리에 의해 감소되거나 제거되거나 혹은 압축력으로 전환될 수 조차 있다. 박막층(5-10nm)이 석출된 후에 석출을 일시적으로 중단시키고, 방사성 플라즈마(O2+argon과 같은 저압의 기체)를 처리하고, 플라즈마 파워(power)를 중단한 후, 석출을 재개한다. 석출과 플라즈마 처리라는 사이클의 반복을 통해 특별한 용도에 필요한 요구사항, 특히 두꺼운 막을 필요로 하는 경우, 이에 필요한 장력이나 압축력을 갖는 두꺼운 층을 만들어낼 수 있다.This tension can be reduced or eliminated by plasma treatment or even converted to compressive force. Precipitation is temporarily stopped after the thin film layer (5-10 nm) is precipitated, the radioactive plasma (a gas of low pressure such as O 2 + argon) is treated, the plasma power is stopped, and precipitation is resumed. Repeating the cycles of precipitation and plasma treatment can produce thick layers with the necessary tension or compressive force, especially if the requirements for a particular application require a thick film.
실시예18Example 18 : 알루미늄 규산염의 : Of aluminum silicate ALDALD 1One
기질 온도 200℃에서 3×10-9moles/cm2양의 트리메틸알루미늄 증기와 3×10-8moles/cm2양의 트리스(tert-부톡시)실라놀 증기를 교대로 이용하여 ALD를 실시한다. 구조식Al2Si16O35을 갖는 투명한 알루미늄 규산염 막이 사이클마다 2nm의 놀랄만큼 빠른 속도로 석출된다. 이들은 약 1.47의 굴절율을 갖는다.In the substrate temperature 200 ℃ 3 × 10 -9 moles / cm 2 amounts of trimethyl aluminum vapor with 3 × 10 - using a 8moles / cm 2 amounts of tris (tert- butoxy) silanol alternately vapor is carried to ALD. A transparent aluminum silicate film having the structure Al 2 Si 16 O 35 precipitates at a surprisingly fast rate of 2 nm per cycle. They have a refractive index of about 1.47.
실시예19Example 19 : 알루미늄 규산염의 : Of aluminum silicate ALDALD
기질 온도 250℃에서 3×10-9moles/cm2양의 트리스(디메틸아미노)알루미늄 증기와 3×10-8moles/cm2양의 트리스(tert-부톡시)실라놀 증기를 교대로 이용하여 ALD를 실시한다. 이 알루미늄 규산염 막은 0.1nm/cycle로 형성되고, 약 1.46의 굴 절율을 갖는다.3 × 10 −9 moles / cm 2 of tris (dimethylamino) aluminum vapor and 3 × 10 −8 moles / cm 2 of tris ( tert -butoxy) silanol vapor are alternately used at a substrate temperature of 250 ° C. Perform ALD. This aluminum silicate film is formed at 0.1 nm / cycle and has a refractive index of about 1.46.
실시예20Example 20 : 알루미늄 규산염의 : Of aluminum silicate ALDALD
트리스(tert-부톡시)실라놀 증기 대신에 트리스(tert-펜틸옥시)실라놀 증기를 사용하여 실시예19를 반복한다. 유사한 결과물이 얻어진다.Tris (tert- butoxy) silanol, instead of playing vapor tris- by (tert-pentyloxy) using a silanol vapor are repeated in Example 19. Similar results are obtained.
실시예21Example 21 : 알루미늄 규산염의 : Of aluminum silicate ALDALD
트리스(디메틸아미노)알루미늄 증기와 트리스(tert-부톡시)실라놀 증기 사이에 수증기를 사용하여 실시예19를 반복한다. 기체가 흐르는 방향을 따라 0.1nm/cycle의 매우 균일한 두께를 갖는 비슷한 막이 얻어진다.Example 19 is repeated using water vapor between tris (dimethylamino) aluminum vapor and tris ( tert -butoxy) silanol vapor. A similar film is obtained with a very uniform thickness of 0.1 nm / cycle along the direction of gas flow.
실시예22Example 22 : : 란탄늄Lanthanum 규산염의 Silicate ALDALD
상기한 바와 같이 도2의 기구를 이용하여 테트라키스(디메틸아미도)하프늄 증기 대신에 트리스(비스(트리메틸실릴)아미도)란탄늄 증기를 사용하여 실시예12를 반복한다. 기질 온도250℃에서 La:Si비가 약2인 투명한 산화물 막이 기질위에 형성된다. 이 막에서는 어떠한 탄소나 질소 성분도 검출되지 않는다. 굴절율은 1.7이고, 두께는 0.1nm/cycle이다.As described above, Example 12 is repeated using tris (bis (trimethylsilyl) amido) lanthanum vapor instead of tetrakis (dimethylamido) hafnium vapor using the apparatus of FIG. At a substrate temperature of 250 ° C., a transparent oxide film having a La: Si ratio of about 2 is formed on the substrate. No carbon or nitrogen component is detected in this film. The refractive index is 1.7 and the thickness is 0.1 nm / cycle.
실시예23Example 23 : : 란탄늄Lanthanum 산화물의 Oxide ALDALD
도 2의 기구를 사용한 트리스(2, 2, 6, 6-테트라메틸피페리디도)란탄늄과 수증기에 교대로 ALD를 시행하면 란탄늄 산화물 막이 형성된다.When ALD is alternately applied to tris (2, 2, 6, 6-tetramethylpiperidido) lanthanum and water vapor using the apparatus of FIG. 2, a lanthanum oxide film is formed.
실시예24Example 24 : 이산화 규소의 Of silicon dioxide ALDALD
테트라이소 시아나토실렌 증기와 트리스(tert-butoxy)실라놀 증기를 교대로 사용하여 ALD를 시행하여 이산화 규소 막을 형성한다. 이러한 반응성이 작은 전구 체를 위하여 보다 큰 노출 속도(fluxes of exposure(>10-7Langmuirs))가 요구된다.ALD is carried out using alternating tetraisocyanatosylene vapor and tert- butoxy silanol vapor to form a silicon dioxide film. Higher exposure rates (fluxes of exposure (> 10 −7 Langmuirs)) are required for these less reactive precursors.
본 발명이 속하는 기술분야의 당업자는 더이상의 일련의 실험없이도, 여기에 특별히 기술된 본 발명의 특정 구현예와 등가의 것을 이용할 수 있음을 인식하거나 확인할 수 있을 것이다. 즉, 그러한 등가의 것도 이하의 청구항의 범주에 포함되어 지는 것이다.Those skilled in the art to which the present invention pertains will recognize or be able to use equivalents to the specific embodiments of the invention specifically described herein without further a series of experiments. In other words, such equivalents are included within the scope of the following claims.
본 발명의 다양한 목적, 특징, 이점들은, 이하의 도면들과의 연관성을 고려하면, 발명의 상세한 설명에 의해 보다 잘 이해될 수 있다. 도면들은 단지 설명을 위한 것이므로 본 발명에 대해 어떠한 제한도 가하지 않는다.Various objects, features, and advantages of the present invention can be better understood by the detailed description of the present invention, in consideration of the connection with the following drawings. The drawings are for illustrative purposes only and do not impose any limitation on the invention.
도 1은 본 발명의 적어도 한 구현예의 수행에 사용되는 원자층 석출 기구의 횡단도이다.1 is a cross-sectional view of an atomic layer precipitation mechanism used to perform at least one embodiment of the present invention.
도 2는 본 발명의 적어도 한 구현예의 수행에 사용되는 원자층 석출 기구의 횡단도이다.2 is a cross-sectional view of an atomic layer precipitation mechanism used to perform at least one embodiment of the present invention.
도 3은 본 발명의 한 구현예를 사용하여 하프늄으로 균일하게 코팅한 실리콘 회로판(silicon wafer)의 구멍들의 전자 현미경 사진을 스캐닝한 횡단도이다.3 is a cross-sectional scanning electron micrograph of the holes of a silicon wafer uniformly coated with hafnium using one embodiment of the present invention.
Claims (3)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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US23628300P | 2000-09-28 | 2000-09-28 | |
US60/236,283 | 2000-09-28 | ||
US25391700P | 2000-11-29 | 2000-11-29 | |
US60/253,917 | 2000-11-29 |
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US20160268121A1 (en) | 2016-09-15 |
US6969539B2 (en) | 2005-11-29 |
US20160111276A1 (en) | 2016-04-21 |
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US9905414B2 (en) | 2018-02-27 |
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US20050277780A1 (en) | 2005-12-15 |
JP2004527651A (en) | 2004-09-09 |
JP5175157B2 (en) | 2013-04-03 |
US20040043149A1 (en) | 2004-03-04 |
US20150118395A1 (en) | 2015-04-30 |
JP5290488B2 (en) | 2013-09-18 |
WO2002027063A2 (en) | 2002-04-04 |
EP1327010B1 (en) | 2013-12-04 |
US20130122328A1 (en) | 2013-05-16 |
EP1772534A3 (en) | 2007-04-25 |
US8334016B2 (en) | 2012-12-18 |
EP1772534A2 (en) | 2007-04-11 |
EP1327010A2 (en) | 2003-07-16 |
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